Perfluorinated amide salts and their uses as ionic conducting materials

ABSTRACT

The invention concerns ionic compounds in which the anionic load has been delocalized. A compound disclosed by the invention is comprised of an amide or one of its salts, including an anionic portion combined with at least one cationic portion M +m  in sufficient numbers to ensure overall electronic neutrality; is the compound is further comprised of M as a hydroxonium, a nitrosonium NO + , an ammonium —NH 4 +, a metallic cation with the valence m, an organic cation with the valence m, or an organometallic cation with the valence m. The anionic portion matches the formula R F —SO x —N-Z, wherein R F  is a perfluorinated group, x is 1 or 2, and Z is an electroattractive substituent. The compounds can be used notably for ionic conducting materials, electronic conducting materials, colorants, and the catalysis of various chemical reactions.

The present invention relates to ionic compounds in which the anioniccharge is delocalized, and there uses.

It is known and it is particularly interesting to introduce ionic groupsin molecules or organic polymers having various functions. Coulombicstresses correspond, indeed, to the stronger interactions which areavailable at the molecular level, and the ionic groups modify in anutmost manner the molecules to which they are bonded. Coloring matterswhich are made soluble in water by means of sulfonate or carboxylatefunctions may be mentioned.

However, the groups of this types, —CO₂ ⁻ 1/mM^(m+) or —SO₃ ⁻ 1/mM^(m+),are not dissociated, and they do not induce solubility in solvents otherthan water or certain highly polar protic solvents such as lightalcohols, which considerably restrict the scope of their utilization.

On the other hand, salts of the compounds [R_(F)SO₂—N—SO₂R_(F)]⁻1/mM^(m+) in which R_(F) is a perfluorinated group and M^(m+) is acation of valence m+ are known, which are soluble and are dissociated inorganic aprotic media or solvating polymers. It is however consideredthat the existence of two perfluoroalkylsulfonyl groups (in particularthe existence of fluorine atoms on the α atom of carbon of each sulfonylgroup) which exert an important attracting power on the electrons of theionic charge, is a necessary condition to obtaining properties ofsolubility and dissociation. For example, the pK_(a) of die acidH[CF₃SO₂—N—SO₂CF₃] is only 1.95, which compares to that of thenon-fluorinated acid CH₃SO₃H (pK_(a)=0.3) and is clearly inferior tothat of perfluorinated acid CF₃SO₃H (pK_(a)<−9) because of the basiccharacter of the central nitrogen atom with respect to the oxygen atomof sulfonic acids.

Surprisingly, the inventors have found that the excellent properties ofsolubility and dissociation of the ionic groups —SO₂—N—SO₂— weremaintained when a single sulfonated group has fluorine atoms on atomswhich are adjacent to the sulfur atom, giving an extremely wide choiceof functional molecules. In a manner also quite unexpected, it has beennoted that it was possible for obtaining the same properties, to omitthe group —SO₂ bound to the non-perfluorinated group provided that thegroup which is directly bound to nitrogen has a Hammett parameter σ*higher than 0.6. By way of comparison, the Hammett parameters σ* of agroup —SO₂— bound to a non-perfluorinated group is 3.5 and 4.55 for agroup CF₃SO₂—.

The present inventors have also found that the sulfonyl —SO₂— groupscould be replaced, with minor variations of properties, by sulfinyl —SO—or phosphonyl —PO═ groups.

It is consequently an object of the present invention to provide afamily of ionic compounds having a good solubility and a gooddissociation, without having to rely on complex modifications of thestarting molecule. The precursors of the molecule of the invention arefound in the form of derivatives of sulfonic acids or of amine groups onthe one hand, and derivatives of perfluorosulfonyl types on the otherhand, which for the most part are industrial products and/or are easilyaccessible. In addition, it should be noted that a decrease of theperfluorinated fraction in the compounds of the invention enables toreduce the production costs of said compounds and consequently the costof the applications in which they are involved.

A compound of the present invention is an ionic compound consisting ofan amide or one of its salts, comprising an ionic part associated withat least a cationic part M^(m+) in sufficient number to ensure anelectronic neutrality to the assembly. It is characterized in thatM^(m+) is a hydroxonium, a nitrosonium NO⁺, an ammonium —NH₄ ⁺, ametallic cation having a valency m, an organic cation having a valencym, or an organo-metallic cation having a valency m, and in that theanionic part corresponds to the formula R_(F)—SO_(x)—N⁻Z, in which:

-   -   the group —SO_(x)— represents a sulfonyl group —SO₂— or a        sulfinyl group —SO—;    -   R_(F) is a halogen or a perhalogenated alkyl, alkylaryl,        oxa-alkyl, aza-alkyl or thia-alkyl radical, or a radical        corresponding to one of the formulae R_(A)CF₂—, R_(A)CF₂CF₂—,        R_(A)CF₂CF(CF₃)— or CF₃C(R_(A))F— in which R_(A)— represents a        non-perhalogenated organic radial;    -   Z represents an electro-attractor radical having a Hammett        parameter at least equal to that of a phenyl radical, and        selected from:    -   j) —CN, —NO₂, —SCN, —N₃, —CF₃, R′_(F)CH₂— (R′_(F) being a pair        of fluorinated radicals, preferably CF₃—), fluoroalkyloxy        radicals, fluoroalkylthioxy radicals,    -   jj) radicals comprising one or a plurality of aromatic nuclei        possibly containing at least one nitrogen, oxygen, sulfur or        phosphorus atom, said nuclei possibly being condensed nuclei        and/or said nuclei possibly carrying at least one substitutent        selected from halogens, —CN, —NO₂, —SCN, —N₃, —CF₃, CF₃CH₂—,        CF₂═CF—O—, perfluoroalkyl groups, fluoroalkyloxy groups,        fluoroalkylthioxy groups, alkyl, alkenyl, oxa-alkyl,        oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl, thia-alkenyl        groups, polymer radicals and radicals having at least one        cationic ionophoric group and/or at least one anionic ionophoric        group;    -   it being understood that a substituent Z may be a monovalent        radical, part of a multivalent radical carrying a plurality of        groups R_(F)—SO_(x)—N—, or a segment of a polymer; or    -   Z is a radical R_(D)—Y— in which Y is a sulfonyl, sulfinyl or        phosphonyl group and RD is a radical selected from the group        consisting of:    -   a) alkyl or alkenyl radicals, aryl, arylalklyl, alkylaryl or        alkenylaryl radicals, alicyclic or heterocyclic radicals,        including polycyclic radicals;    -   b) alkyl or alkenyl radicals comprising at least one functional        ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy,        silyl, isocyanate or thioisocyanate functional group;    -   c) aryl, arylakyl, arylalkenyl, alkylaryl or alkenylaryl        radicals, in which the aromatic nuclei and/or at least one        substitutent of the nucleus comprises heteroatoms such as        nitrogen, oxygen, sulfur;    -   d) radicals comprising condensed aromatic cycles which possibly        comprise at least one heteroatom selected from nitrogen, oxygen,        sulfur;    -   e) halogenated alkyl, alkenyl, aryl, arylalkyl, alkylaryl or        alkenylaryl radicals in which the number of carbon atoms        carrying at least one halogen is at most equal to the number of        non-halogenated carbon atoms, the x carbon of group Y not being        halogenated when Y is —SO₂—, said radicals possibly comprising        functional ether, thioether, amine, imine, carboxyl, carbonyl,        hydroxy, silylalkyl, silylaryl, isocyanate or isothiocyanate        groups;    -   f) radicals R_(c)(R′)(R″)—O— in which R_(c) is a perfluorinated        alkyl radical and R′ and R″ are independently from one another        an hydrogen atom or a radical such as defined in a), b), c)        or d) above [for example CF₃CH₂O—, (CF₃)₃CO—, (CF₃)₂CHO—,        CF₃CH(C₆H₅)O—, —CH₂(CF₂)₂CH₂—];    -   g) radicals (R_(B))₂N—, in which the radicals R_(B) are        identical or different and are as defined in a), b), c), d)        and e) above, one of the R_(B) could be an hydrogen atom or the        two radicals R_(B) together forming a bivalent radical which        constitutes a cycle with N;    -   h) radicals constituted by a polymer chain;    -   i) radicals having one or more cationic ionophoric groups and/or        one or more anionic ionophoric groups;    -   it being understood that a substituent R_(D) could be a        monovalent radical, part of a multivalent radical carrying a        plurality of groups R_(F)—SO_(x)—N—Y—, or a segment of a        polymer;    -   it being understood that when Y is a sulfonyl and when R_(D) is        a radical as defined in a), R_(F) is R_(A)CF₂—, R_(A)CF₂CF₂—,        R_(A)CF₂CF(CF₃)—, CF₃C(R_(A))F— or a perhaloalkyl radical having        1 to 2 carbon atoms not favouring a phase separation due to the        aggregation of the fluorinated segments.

In a compound of the present invention, the cation may be a metalliccation selected from cations of alkali metals, cations of alkali-earthmetals, cations of transition metals, cations of tri-valent metals,cations of a rare earth. Bt way of example, Na⁺, Li⁺, K⁺, Sm³⁺, La³⁺,Ho³⁺, Sc³⁺, Al³⁺, Y³⁺, Yb³⁺, Lu³⁺, Eu³⁺ may be cited.

The cation may also be an organo-metallic cation, for example ametallocenium. By way of example, there may be mentioned the cationsderived from ferrocene, titanocene, zirconocene, indenocenium or ametallocenium arene, cations of transition metals complexed with ligandsof a phosphine type possibly having a chirality, organo-metallic cationshaving one or more alkyl or aryl groups co-valently fixed to an atom ora group of atoms, such as methylzinc, phenylmercury, trialkyltin ortrialkyllead cations. The organo-metallic cations may be part of apolymer chain.

According to a variant of the invention, the compounds of the inventionhave an organic cation selected from the group consisting of R₃O⁺(oxonium), NR₄ ⁺ (ammonium), RC(NHR₂)₂+ (amidinium), C(NHR₂)₃+(guanidinium), C₅R₆N⁺ (pyridinium), C₃R₅N₂+(imidazolium),C₃R₇N₂+(imidazolinium), C₂R₄N₃ ⁺ (triazolium), SR₃ ⁺ (sulfonium), PR₄ ⁺(phosphonium), IR₂ ⁺ (iodonium), (C₆R₅)₃C+ (carbonium) cations. In agiven cation, the radicals R may all be identical. However, a cation mayalso include radicals R which are different from one another. A radicalR may be a H or it may be selected from the following radicals:

-   -   alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl,        thia-alkyl, thia-alkenyl, sila-alkyl, sila-alkenyl, aryl,        arylalkyl, alkyl-aryl, alkenyl-aryl, dialkylamino and dialkylazo        radicals;    -   cyclic or heterocyclic radicals possibly comprising at least one        lateral chain comprising heteroatoms such as nitrogen, oxygen,        sulfur;    -   cyclic or heterocyclic radicals possibly comprising heteroatoms        in the aromatic nucleus;    -   groups comprising a plurality of aromatic or heterocyclic,        condensed or non-condensed nuclei, possibly containing at least        one nitrogen, oxygen, sulfur or phosphorus atom.

When an onium cation carries at least two radicals R which are differentfrom H, these radicals may constitute together a cycle which is aromaticor non-aromatic, possibly enclosing the center carrying the cationiccharge.

When the cationic part of a compound of the invention is an oniumcation, it may be either in the form of an independent cationic groupwhich is bound to the anionic part only by the ionic bond between thepositive charge of the cation and the negative charge of the anionicpart. In this case, the cationic part may be part of a recurring unit ofa polymer.

An onium cation may also be part of the radical Z or the radical RDcarried by the anionic centre. In this case, a compound of the inventionconstitutes a zwitterion.

When the cation of a compound of the invention is an onium cation, itmay be selected so that it can introduce into the compound substituentspermitting to confer specific properties to said compound. For example,the cation M⁺ may be a cationic heterocycle with aromatic character,including at least one alkylated nitrogen atom in the cycle. By way ofexample, there may be cited an imidazolium, a triazolium, a pyridinium,a 4-dimethylamino-pyridinium, said cations possibly carrying asubstituent on the carbon atoms of the cycle. Among these cations, thosewhich give an ionic compound according to the invention in which themelting point is lower than 150° C. are particularly preferred. Such acompound having a low melting point is particularly useful for thepreparation of materials with protonic conduction. A material withprotonic conduction which is particularly preferred comprises a compoundaccording to the invention in which the cation is formed by addition ofa proton on the nitrogen of an imidazoline, an imidazole or a triazole,as well as the nitrogenated corresponding base in a proportion of 0.5 to10 in molar ratio.

A compound of the invention in which the cation M is a cationic grouphaving a bond —N═N—, —N═N+, a sulfonium group, an iodonium group, or asubstituted or non-substituted arene-ferrocenium cation, possiblyincorporated in a polymeric network, is interesting insofar as it can beactivated by a source of actinic energy of suitable wavelength.Particular examples of such compounds include those in which the cationis a diaryliodonium, dialkylaryliodonium, triarylsulfonium, trialkylarylsulfonium, or phenacyl-dialkyl sulfonium radical which is substituted ornon-substituted. The above cations may be part of a polymer chain.

The cation M of a compound of the invention may include a group2,2′[azobis(2-2′-imidazolinio-2-yl)propane]²⁺ or2,2′-azobis(2-amidiniopropane)²⁺. The compound of the invention is thencapable of releasing, under the action of heat or an ionizing radiation,radicals which enable initiation of polymerization, cross-linkingreactions or, in a general manner, chemical reactions involving freeradicals. Moreover, these compounds are easily soluble in polymeric andmonomeric organic solvents even of low polarity, contrary to thederivatives of anions of the type Cl⁻ normally associated with this typeof compounds. On the other hand, they have a negligible vapour pressurecontrary to the other radical initiators of the peroxide or azo type,which is a considerable advantage for the preparation of thin polymerfilms, the volatility of the initiator having as a consequence a badpolymerization or cross-linking of the surface of the film.

In an embodiment of the invention, R_(F) is a fluorine atom or a pair ofhalogenated alkyl radicals preferably having from 1 to 12 carbon atoms,or a pair of halogenated alkylaryl radicals preferably having from 6 to9 carbon atoms. The pair of halogenated alkyl radicals may be a linearor branched radical. In particular, radicals in which the carbon atomwhich will be in α position with respect to the group —SO_(x)— carriesat least one fluorine atom, may be cited. Examples of such radicalsinclude R_(A)CF₂—, R_(A)CF₂CF₂—, R_(A)CF₂CF(CF₃)— or CF₃C(R_(A))F— inwhich R_(A) represents a non-perhalogenated organic radical, an alkylgroup, an aryl group, an alkylaryl or arylalkyl group; a groupcomprising at least one ethylenic unsaturation and/or a condensablegroup and/or a dissociable group; a mesomorphous group; a chromophorousgroup; a self-doped electronic conductive polymer; a hydrolyzablealkoxysilane; a polymer chain carrying grafts including a carbonylgroup, a sulfonyl group, a thionyl group or a phosphonyl group; a groupcapable of trapping free radicals such as a crowded phenol or a quinone;a dissociating dipole such as an amide, a sulfonamide or a nitrile; aredox pair such as a disulfide, a thioamide, a ferrocene, apheno-thiazine, a bis(dialkylaminoaryl) group, a nitroxide or anaromatic imide; a complexing ligand; a zwitterion, an optically orbiologically active amino acid or a polypeptide; a chiral group.

The choice of substituent Z enables to adjust the properties of acompound of the invention.

A particular family of compounds of the invention is the one in which Zrepresents a group R_(D)Y—. The compounds in which Y is —SO₂— areespecially preferred.

In an embodiment, R_(D) is selected from alkyl, alkenyl, oxa-alkyl,oxa-alkenyl, aza-alkyl, aza-alkenyl, thia-alkyl or thia-alkenyl radicalshaving from 1 to 24 carbon atoms, or from aryl, arylalkyl, alkylaryl oralkenylaryl radicals having from 5 to 24 carbon atoms.

In another embodiment, R_(D) is selected from alkyl or alkenyl radicalshaving from 1 to 12 carbon atoms and possibly comprising at least oneheteroatom O, N or S in the main chain or in a lateral chain, and/orpossibly carrying a hydroxy group, a carbonyl group, an amino group or acarboxyl group.

A substituent R_(D) may be a polymer radical, for example anoligo(oxyalkylene) radical. The compound of the invention then appearsin the form of a polymer carrying an ionic group —[Y—N—SO_(x)—R_(F)]⁻,M⁺.

R_(D) may be a recurring unit of a polymer, for example an oxyalkyleneunit or a styrene unit. The compound of the invention then appears inthe form of an polymer in which at least part of the recurring unitscarry a lateral group on which an ionic group —[Y—N—SO_(x)—R_(F)]⁻, M⁺is bonded. By way of example, a poly(oxyalkylene) in which at leastcertain oxyalkylene units carry a substituent —[Y—N—SO_(x)—R_(F)]⁻, M⁺,or a polystyrene in which at least certain styrene units carry asubstituent —[Y—N—SO_(x)—R_(F)]⁻, M⁺, for example[styrenyl-Y—N—S(O)_(x)—R_(F)]⁻, may be mentioned.

A particular category of compounds of the invention comprises thecompounds in which the substituent R_(D) has at least one anionicionophoric group and/or at least one cationic ionophoric group. Theanionic group may for example be a carboxylate (—CO₂—), a sulfonatefunction (—SO₃—), a sulfonimide function (—SO₂NSO₂—) or a sulfonamidefunction (—SO₂N—). The cationic ionophoric group may for example be aniodonium, sulfonium, oxonium, ammonium, amidinium, guanidinium,pyridinium, imidazolium, imidazolinium, triazolium, phosphonium orcarbonium group. The cationic ionophoric group may totally or partiallyplay the role of the cation M.

When R_(D) includes at least ethylenic unsaturation and/or a condensablegroup and/or a group which is dissociable by thermal or photochemicalmeans or by ionic dissociation, the compounds of the invention arereactive compounds which may be subject to polymerizations,cross-linkings or condensations, optionally with other monomers. Theymay also be used to fix ionophoric groups on the polymers carrying asuitable reactive function.

A substituent R_(D) may be a mesomorphous group or a chromophorous groupor a self-doped electronically conductive polymer or a hydrolyzablealkoxysilane.

A substituent R_(D) may include a group capable of trapping freeradicals, for example, a hindered phenol or a quinone.

A substituent R_(D) may also include a bipolar dissociating agent, forexample, an amide function, a sulfonamide function or a nitrilefunction.

A substituent R_(D) may also include a redox couple, for example, adisulfide group, a thioamide group, a ferrocene group, a phenothiazinegroup, a bis(dialkylaminoaryl) group, a nitroxide group or an aromaticimide group.

A substituent R_(D) may also include a complexing ligand or an opticallyactive group.

Another category of compounds of the invention comprises compounds inwhich R_(D)—Y— represent an amino acid, or an optically or biologicallyactive polypeptide.

According to a variant, a compound of the invention comprises asubstituent R_(D) which represents a radical having a valency v higherthan 2, itself including at least one group R_(F)—S(O)_(x)—N—Y—. In thiscase, the negative charges present on the anionic part of the compoundof the invention should be compensated by an appropriate number ofcations or ionophorous cationic groups M.

When a compound of the present invention corresponds to the formulaR_(F)—S(O)_(x)—N-Z, in which Z is an electroattractive group which isnot bonded to the nitrogen which carries the negative charge by a groupY, Z is advantageously selected from the group consisting of —CN,—OC_(n)F_(2n+1), —OC₂F₄H, —SC_(n)F_(2n+1) and —SC₂F₄H, —O—CF═CF₂,—SCF═CF₂, n being a whole number from 1 to 8. Z may also be a radicalC_(n)F_(2n+1)CH₂—, n being a whole number from 1 to 8, or among theheterocyclic compounds, in particular those derived from pyridine,pyrazine, pyrimidine, oxadiazole, thiadiazole, which are fluorinated ornon-fluorinated. Z may also represent a recurring unit of a polymer. Thecompound of the invention is then in the form of a polymer in which atleast part of the recurring units carry a lateral group on which anionic group —[(N—SO_(x)—R_(F))⁻, M⁺] is fixed. By way of example, apolymer comprising one of the following recurring units may bementioned:

or a polyzwitterion of a conductive polymer which is a self-dopedpolyaniline in which the recurring unit is:

The compounds of the invention may be obtained, by a process in which acompound R_(F)SO_(x)-L is reacted with a compound [A-N-Z]^(n−) _(m)nM^(m+), R_(F), x, M and Z being as previously defined, L representingan electronegative starting group such as a halogen, a N-imidazoylradical, a N-triazoyl radical, a radical R_(F)SO_(x+1)— and A representsa cation M^(m+), a trialkylsilyl group, a trialkylgermanyl group, atrialkylstannyl group or a tertiaryalkyl group, in which the alkylsubstituents have from 1 to 6 carbon atoms. By way of example, thereaction of a fluorosulfonyl fluoride with a bi-salt of cyanamideaccording to the following reaction scheme may be mentioned:FSO₂—F+[NaNCN]⁻a Na⁺

NaF+[FSO2-NCN]⁻Na⁺.

The reaction of a substituted aniline with trifluoromethanesulfonicanhydride may also be mentioned.

The compounds in which Z represents R_(D)Y— may be obtained by a processin which a compound R_(D)-Y-L is reacted with a compound[R_(F)SO_(X)—N-A]^(n−) _(m) nM^(m+). By way of example of such aprocess, the reaction of a perfluorosulfonamide or one of its salts witha sulfonyl halide may be mentioned.

The use of a compound [A-N-Z]^(n−) _(m) nM^(m+) in which A is a tertiaryalkyl group is advantageous, because such a group is a proton precursorby formation of the corresponding alkene. The use of a trialkylsilyl isespecially interesting when the starting group is a fluorine atom, byreason of the very high stability of the bond F—Si.

When there is used a compound [A-N-Z]^(n−) _(m) nM^(m+) in which A isthe proton, it is advantageous to carry out the reaction in the presenceof a tertiary base or crowded base T capable of forming the salt L⁻(HT⁺)by combination of the proton, in order to promote the formation of thecompound of the invention. The base may be selected from alkylamines(for example triethylamine, diisopropylamine, quinuclidine),1,4-diazobicyclo[2,2,2]octane (DABCO); pyridines (for example pyridine,alkylpyridines, dialtrylaminopyridines); imidazoles (for exampleN-alkylimidazoles, imidazo[1,1-a]pyridine); amidines (for example1,5-diazabicyclo[4,3,O]non-5-ene (DBN),1,8-diazabicyclo[5,4,O]undec-7-ene (DBU)); guanidines (for exampletetramethyl guanidine,1,3,4,7,8-hexahydro-1-methyl-2H-pyrimido[1,2-a]pyrimidine (HPP).

By way of example of such a process, the process in which a sulfonylchloride R_(D)SO₂Cl is reacted with a perfluorosulfonanmide in thepresence of DABCO may be mentioned.

A compound according to the invention may also be obtained by reactingperfluorosulfonic acid or one of its salts with a compound (R^(i))₃P═N-Zin which the R^(i) represent independently from one another an alkylradical, an aryl radical or a dialkylamino radical. In the same manner,an acid R_(D)SO_(x)—OH or one of its salts may be reacted with acompound (R^(i))₃P═N—SO_(x)R_(F). By way of example, the reaction of asodium alkylsulfonate with R_(F)SO₂N═P(C₆H₅)₃ may be mentioned.

The cation of a compound obtained according to either one of theprocesses described above may be replaced by known processes of cationexchange, either by precipitations or selective extractions, or by theuse of ion exchange resins.

In addition, the substituent R_(D) of a compound of the invention may bemodified by means of known reactions. For example, a substituent R_(D)which comprises an allyl group may be converted by reaction with aperoxide to give an epoxidized substituent R_(D). A group —NHR may beconverted into a vinylester group by reaction with a strong base such aspotassium tert-butoxide, then with vinylchloroformate. The processesenabling to carry out these modifications and others are available tothose skilled in the art. Of course, the functions carried by radicalR_(A) and R which could interfere with the reactions leading to thepreparation of the compounds of the invention may be temporarilyprotected by means of known techniques. For example, an amine functionmay be protected by a group t-BOC (tertiobutoxycarbonyl) which is stablein the presence of bases T but which is easily removed by treatment inan acid medium.

The ionic compounds of the present invention comprise at least oneionophoric group on which substituents which can vary to a large extentare fixed. Taking into account the large choice possible for thesubstituents, the compounds of the invention enable the production ofproperties of ionic conduction in most of the organic media, liquids orpolymers having even a low polarity. The applications are important inthe field of electrochemistry, in particular for storing energy inprimary or secondary generators, in supercapacitances, in combustiblebatteries and in electroluminescent diodes. The compatibility of theionic compounds of the invention with polymers or organic liquids enableto induce noted anti-static properties, even when the content of ioniccompound is extremely low. The compounds of the invention which arepolymers, as well as polymer compounds obtained from the compounds ofthe invention having the property of polymerizing or co-polymerizing,show the properties mentioned above with the advantage of having animmovable anionic charge. This is why another object of the presentinvention resides in an ionically conductive material consisting of anionic compound of the present invention in solution in a solvent.

In an embodiment, the ionic compound used for the preparation of anionically conductive material is selected from the compounds in whichthe cation is ammonium or a cation derived from a metal, in particularlithium or potassium, zinc, calcium, metals of rare earths, or anorganic cation, such as a substituted ammonium, an imidazolium, atriazolium, a pyridinium a 4-dimethylamino-pyridinium, said cationsoptionally carrying a substituent on the carbon atoms of the cycle. Theionically conductive material thus obtained has an elevated conductivityand solubility in solvents, resulting from weak interactions between thepositive charge and the negative charge. Its field of electrochemicalstability is extended, and it is stable in reducing as well as oxidizingmedia. Moreover, the compounds which have an organic cation and amelting point lower than 150° C., in particular imidazolium, triazolium,pyridinium, 4-dimethylamino-pyridinium compounds have an intrinsicelevated conductivity, even in the absence of solvent, when they are inmolten phase.

The materials with ionic conduction which incorporate a compound of theinvention in which R_(F) is a fluorine atom or a perhalogenated alkylradical having from 1 to 12 carbon atoms, or a perhalogenated alkylarylradical having from 6 to 9 carbon atoms are interesting to the extentthat the low interactions between the atoms of fluorine of the chainresult in high solubility and conductivity, even in the case where theremainder of the molecule contains groups having a tendency to givestrong interactions such as conjugated aromatic radicals or zwitterions.

The choice of a compound of the invention in which R_(F) is selectedfrom the radicals R_(A)CF₂—, R_(A)CF₂CF₂—, R_(A)CF₂CF(CF₃)— orCF₃C(R_(A))F— enable it to very precisely adapt the properties of theionically conductive material by selecting the substituent R_(A) in anappropriate manner. In particular, they permit to rely, with a reducednumber of fluorine atoms, on the properties of dissociation and ofsolubility inherent to the anionic charges of the perfluorinatedsystems. These groups are easily accessible from industrial productssuch as tetrafluoroethylene or tetrafluoropropylene. The reducedquantity of fluorine renders these compounds less susceptible toreduction by metals which are even electropositive, such as aluminium,magnesium or especially lithium.

The properties of the ionically conductive material may also be adaptedis by the choice of the substituent R_(D).

The choice for R_(A) or R_(D) of an alkyl group, an aryl group, analkylaryl group or an arylalkyl group, enables to introduce into theionically conductive material properties of mesogene type, in particularalkyl groups having from 6 to 20 carbon atoms, aryl-alkyl groups, inparticular those containing the biphenyl entity which form phases of theliquid crystal type. Properties of conduction in phases of the liquidcrystal, nematic, cholesteric or discotic types, are interesting forapplications relating to optical posting or to reduce the mobility ofanions in the electrolytes, in particular in polymer electrolytes,without affecting the mobility of the cations. This characteristic isimportant for applications in electrochemical generators, andparticularly those involving lithium cations.

When the substituent R_(A) is a mesomorphous group or a group comprisingat least one ethylenic unsaturation and/or a condensable group and/or agroup which is dissociable by thermal means, by photochemical means orby ionic dissociation, or when R_(D) is a substituent containing one ofthese groups, the ionically conductive material easily forms polymers orcopolymers which are polyelectrolytes, either intrinsically when thepolymer carries solvating groups, or by addition of a polar solvent of aliquid or polymer type, or by mixture with such a solvent. Theseproducts have a conductivity which is solely due to the cations, whichconstitutes a property which is very useful in the applications of theelectrochemical generator type. In low molar fraction in a copolymer,they produce antistatic properties which are stable and are littledependent on humidity, and promote the fixation of cationic coloringmaterials, this property being useful for textile fibres and lasers withcoloring materials.

The presence of a substituent R_(A) or R_(D) which is a self-dopedelectronically conductive polymer improves the stability of theionically conductive material as compared to outside agents. Theconductivity is stable in time, even at elevated temperatures. Incontact with metals, these materials give very low interface resistanceand, in particular, protect ferrous metals or aluminum againstcorrosion.

When the substituent R_(A) or R_(D) is an hydrolyzable alkoxysilane, theionically conductive material may form stable polymers by the simplemechanism of hydrolysis-condensation in the presence of water, therebyenabling treatment of oxide, silica, silicate, in particular glasssurfaces to induce properties of surface conduction, antistaticproperties, or to promote the adhesion of polar polymers.

When the substituent R_(A) or R_(D) is a group comprising a free radicaltrap such as a congested phenol or a quinone, the ionically conductivematerial has the following advantages and properties: it acts as anantioxidant with no volatility and being compatible with polar monomersand polymers, to which it additionally provides antistatic properties.

When the substituent R_(A) or R_(D) comprises a dissociating dipole suchas an amide, a sulfonamide or a nitrile, the ionically conductivematerial has an improved conductivity in media with low or averagepolarity, in particular in solvating polymers, which enables tominimize, even to remove the addition of solvents or volatileplasticizing agents.

The presence of a substituent R_(A) or R_(D) which contains a redoxcouple such as a disulfide, a thioamide, a ferrocene, a pheno-thiazine,a bis(dialkylaminoaryl) group, a nitroxide, an aromatic imide, enablesintroduction into the ionically conductive material shuttle redoxproperties which are useful as an element for the protection and theequalization of the charge of electrochemical generators, inphotoelectrochemical systems, in particular for converting light intoelectricity, in systems for modulating light of the electrochrome type.

The presence of a substituent R_(A) or R_(D) which is a complexingligand in an ionically conductive material enables chelation of metalliccations, in particular those which possess an elevated charge (2, 3 and4), in the form of a complex which is soluble in organic media,including aprotic media, and enable transportation of these cations inparticular in the form of an anionic complex, in solvating polymers. Themetallic cations of elevated charge are indeed immovable in solvatingpolymers. This type of complexing gives redox couples which areparticularly stable, with certain cations of transition metals (Fe, Co .. . ) or certain rare earths (Ce, Eu . . . ).

The ionically conductive materials containing a compound of theinvention in which R_(D) is an alkyl or an alkenyl substituent whichcontains at least one heteroatom selected from O, N and S have acomplexing and plasticizing property, in particular in polar polymersand especially polyethers. The heteroatoms N and S are selectivelycomplexing for cations of transition metals, Zn and Pb.

When a substituent R_(D) alkyl or alkenyl additionally carries anhydroxy group, a carbonyl group, an amino group, a carboxyl group, anisocyanate group or a thioisocyanate group, the ionic compound of theinvention may give by polycondensation a polymer or copolymer and theionically conductive material which contains such a polymer or copolymershows polyelectrolyte properties.

The presence, in the ionically conductive material of the invention, ofa compound in which R_(D) is selected from radicals aryl, arylalkyl,alkylaryl or alkenylaryl, in which the lateral chains and/or thearomatic nuclei comprise heteroatoms such as nitrogen, oxygen, sulfur,improves dissociation and increases the possibility of forming complexesdepending on the position of the heteroatom (pyridine), or of giving byduplicating oxidation conjugated polymers or copolymers (pyrrol,thiophene).

When the ionically conductive material contains a compound of theinvention in which R_(D) represents a recurring unit of a polymer chain,the material constitutes a polyelectrolyte.

A compound of the invention in which the substituent Z is selected fromthe group consisting of —OC_(n)F_(2n+1), —OC₂F₄H, —SC_(n)F_(2n+1) and—SC₂F₄H, —OCF═CF₂, —SCF═CF₂, n being a whole number from 1 to 8, is aprecursor of stable monomers and polymers in particular towards oxygeneven at temperatures higher than 80° C. when dealing with polymers. Anionically conductive material which contains such a compound istherefore particularly suitable as as electrolyte of a combustiblebattery.

An ionically conductive material of the present invention comprises anionic compound of the invention in solution in a solvent.

The solvent may be an aprotic liquid solvent, a polar polymer or amixture thereof.

The aprotic liquid solvent is selected for example among linear ethersand cyclic ethers, esters, nitriles, nitro derivatives, amides,sulfones, sulfolanes, alkylsulfamides and partially halogenatedhydrocarbons. Particularly preferred solvents include diethylether,dimethoxyethane, glyme, tetrahydrofurane, dioxane,dimethyltetrahydrofurane, methylformate or ethylformate, propylene orethylene carbonate, alkyl carbonates (such as dimethyl carbonate,diethyl carbonate and methylpropyl carbonate), butyrolactones,acetonitrile, benzonitrile, nitromethane, nitrobenzene,dimethylformamide, diethylformamide, N-methylpyrrolidone,dimethylsulfone, tetramethylene sulfone and tetraalkylsulfonamideshaving from 5 to 10 carbon atoms.

The polar polymer may also be selected from a cross-linked or noncross-linked solvating polymer, with or without grafted ionic groups. Asolvating polymer is a polymer which includes solvating units containingat least one heteroatom selected from sulfur, oxygen, nitrogen andfluorine. By way of example of solvating polymers, there may bementioned polymers with linear structure, comb or block type, which mayor may not form a network, based on poly(ethylene oxide), or copolymerscontaining an ethylene oxide, propylene oxide or allylglycidyletherunit, polyphorphazenes, cross-linked network based on polyethyleneglycol cross-linked with isocyanates, or networks obtained bypolycondensation and carrying groups which permit the incorporation ofcross-linkable groups. Block copolymers in which certain blocks carryfunctions which have redox properties may also be mentioned. Of course,the above list is not limiting, and all the polymers having solvatingproperties may also be used.

An ionically conductive material of the present invention maysimultaneously comprise an aprotic liquid solvent selected from theabove-mentioned aprotic liquid solvents and a polar polymer solventcomprising units containing at least one heteroatom selected fromsulfur, nitrogen, oxygen and fluorine. It may comprise 2 to 98% liquidsolvent. By way of example of such a polar polymer, polymers whichmainly contain units derived from acrylonitrile, vinylidene fluoride,N-vinylpyrolidone or methyl methacrylate may be mentioned. Theproportion of aprotic liquid in the solvent may vary from 2%(corresponding to a plasticized solvent) to 98% (corresponding to agelled solvent).

An ionically conductive material of the present invention mayadditionally contain a salt commonly used in the prior art for preparingan ionically conductive material. Among the salts which may be used inadmixture with an ionic compound according to the invention, a saltselected from the perfluoroalcanesulfonates,bis(perfluoroalkylsulfonyl)imides, bis(perfluoroalkylsulfonyl)methanesand tris(perfluoroalkylsulfonyl)methanes is particularly preferred.

Of course, an ionically conductive material of the invention mayadditionally contain the additives known to be used with this type ofmaterial, for example mineral or organic charges in the form of a powderor fibres.

An ionically conductive material of the invention may be used as anelectrolyte in an electrochemical generator. It is therefore an objectof the present invention to provide an electrochemical generatorcomprising a negative electrode and a positive electrode, both beingseparated by an electrolyte, wherein the electrolyte is an ionicallyconductive material as defined above. According to a particularembodiment, such a generator comprises a negative electrode consistingof metallic lithium, or one of its alloys, optionally in the form ofnanometric dispersion in lithium oxide, or a double nitride of lithiumand a transition metal, or an oxide with low potential having thegeneral formula Li_(1+y+x/3)Ti_(2−x/3)O₄ (0≦x≦1, 0≦y≦1), or carbon andcarbonated products resulting from pyrolysis of organic materials.According to another embodiment, the generator comprises a positiveelectrode selected from vanadium oxide VO_(x) (2≦x≦2.5), LiV₃O₈,Li_(y)Ni_(1−x)Co_(x)O₂, (0≦x≦1, 0≦y≦1), magnesium spinelsLi_(y)Mn_(1−x)M_(x)O₂ (M=Cr, Al, V, Ni, 0≦x≦0.5; 0≦y≦2), organicpolydisulfides, FeS, FeS₂, ferric sulfate Fe₂(SO₄)₃, phosphates andphosphosilicates of iron and of lithium of olivine structure, orproducts wherein iron is substituted by manganese, used alone or inadmixtures. The collector of the positive electrode is preferablyaluminum.

An ionically conductive material of the present invention may also beused in a supercapacitance. Another object of the present invention isconsequently a supercapacitance utilizing at least one carbon electrodewith high specific surface, or an electrode containing a redox polymer,in which the electrolyte is an ionically conductive material as definedabove.

An ionically conductive material of the present invention may also beused for the p or n doping of a polymer with electronic conduction andthis use constitutes another object of the present invention.

In addition, an ionically conductive material of the present inventionmay be used as an electrolyte in an electrochrome device. Anelectrochrome device in which the electrolyte is an ionically conductivematerial according to the invention is another, object of the presentinvention.

It has been noted that the strong dissociation of the ionic species ofthe compounds of the invention result in a stabilization of thecarbocations, in particular those in which there is a conjugation withoxygen or nitrogen and, surprisingly in a strong activity of theproponic form of the compounds of the invention on certain monomers. Itis also an object of the invention to provide for the utilization of theionic compounds as photoinitiators which constitute sources of Brønstedacids, catalysts for the polymerization or cross-lining of monomers orprepolymers capable of cationic reaction, or as a catalysts for themodification of polymers.

The process of polymerization or cross-linking of monomers orprepolymers capable of cationic reaction is characterized in that thereis used a compound of the invention as photoinitiator constituting asource of acid which catalyzes the polymerization reaction. Thecompounds according to the invention in which the cation is a grouphaving a bond —N═N⁺, —N═N—, a sulfonium group, an iodonium group, or anoptionally substituted arene-ferrocenium cation, possibly incorporatedin a polymeric skeleton, are particularly preferred.

The choice of substituent R_(F) on the one hand, and of substituentsR_(D) or Z on the other hand, is made in a manner to increase thesolubility of said compound in the solvents used for the reaction of themonomers or prepolymers, is and as a function of the desired propertiesfor the final polymer. For example, the choice of a non-substitutedalkyl radicals gives solubility in low polar media. The choice ofradicals comprising a group oxa or a sulfone gives solubility in polarmedia. The radicals including a sulfoxide group, a sulfone group, and aphosphine oxide group, a phosphonate group, respectively obtained by theaddition of oxygen on the atoms of sulfur or phosphorus, may provideimproved properties with respect to adhesion, glossiness, resistance tooxidation or UV to the polymer obtained. The monomers and polymers whichmay be polymerized or cross-linked by means of the photoinitiators ofthe present invention are those which may be subject to a cationicpolymerization.

Among the monomers, those which include a cyclic ether function, acyclic thioether function or a cyclic amino function, vinyl compounds(more particularly vinyl ethers), oxazolines, lactones and lactames maybe mentioned.

Among the monomers of the cyclic ether or thioether type, ethyleneoxide, propylene oxide, oxetane, epichlorhydrin, tetrahydrofurane,styrene oxide, cyclohexene oxide, vinylcyclohexene oxide, glycidol,butylene oxide, octylene oxide, glycidyl ethers and esters (for exampleglycidyl methacrylate or acrylate, phenyl glycidyl ether, bisphenol Adiglycidylether or its fluorinated derivatives), cyclic acetals havingfrom 4 to 15 carbon atoms (for example dioxolane, 1,3-dioxane,1,3-dioxepane) and spiro-bicyclo dioxolanes may be mentioned.

Among the vinyl compounds, vinyl ethers constitute a very importantfamily of monomers which are subject to cationic polymerization. By wayof example, there may be mentioned ethyl vinyl ether, propyl vinylether, isobutyl vinyl ether, octadecyl vinyl ether, ethyleneglycolmonovinyl ether, diethyleneglycol divinyl ether, butanediol monovinylether, butanediol divinyl ether, hexanediol divinyl ether,ethyleneglycol butyl vinyl ether, triethyleneglycol methyl vinyl ether,cyclohexanedimenthanol monovinyl ether, cyclohexanedimethanol divinylether, 2-ethylhexyl vinyl ether, poly-THF-divinyl ether having a weightbetween 150 and 5000, diethyleneglycol monovinyl ether,trimethylolpropane trivinyl ether, aminopropyl vinyl ether, and2-diethylaminoethyl vinyl ether.

Other vinyl compounds may include by way of example 1,1-dialkylethylenes(for example isobutene), aromatic vinyl monomers (for example styrene,x-alkylstyrene, such as α-methylstyrene, 4-vinylanisole, acenaphthene),N-vinyl compounds (for example N-vinylpyrolidone or N-vinylsulfonamides).

Among the prepolymers, there may be mentioned the compounds in which theepoxy groups are carried by an aliphatic chain, an aromatic chain, or aheterocyclic chain, for example glycidyl ethers or bisphenol A which areethoxylated by 3 to 15 ethylene oxide units, siloxanes having lateralgroups of the type epoxycyclohexene-ethyl obtained by hydrosilylation ofcopolymers of dialkyl, alkylaryl or diaryl siloxane with methylhydrogenosiloxane in the presence of vinylcyclohexene oxide,condensation products of the type sol-gel obtained from triethoxy ortrimethoxy silapropylcyclohexene oxide, urethanes incorporating reactionproducts of monovinylether butanediol and an alcohol of a functionhigher than or equal to 2 with an aliphatic or aromatic di or triisocyanate.

The process of polymerization according to the invention consists inmixing at least one monomer or prepolymer capable of cationicpolymerization and at least one ionic compound of the invention, andsubjecting the mixture obtained to actinic or β radiation. Preferably,the reaction mixture is subjected to irradiation after having beenshaped as a thin layer having a thickness lower than 5 mm, preferably inthe form of a thin film having a thickness lower than or equal to 500μm. The duration of the reaction depends on the thickness of the sampleand the power of the source at the active wavelength λ. It is defined bythe speed in front of the source, which is comprised between 300 m/minand 1 cm/min. Layers of final material having a thickness higher than 5mm may be obtained by repeating many times the operation consisting ofspreading a layer and treating it byu irradiation.

Generally, the quantity of photoinitiator used is between 0.01 and 15%by weight with respect to the weight of the monomer or prepolymer,preferably between 0.1 and 5% by weight.

An ionic compound of the present invention may be used as photoinitiatorin the absence of solvent, for example when it is intended to polymerizeliquid monomers in which the ionic compound used as photoinitiator issoluble or easily dispersible. This type of use is particularlyinteresting, since it permits to get rid of problems associated withsolvents (toxicity, flammability).

An ionic compound of the present invention may also be used asphotoinitiator in the form of a homogenous solution in a solvent whichis insert during polymerization, which solution is ready to use andeasily dispersible, in particular in the case where the mixture to bepolymerized or cross-linked has a high viscosity.

As an example of inert solvent, there may be mentioned volatilesolvents, such as acetone, methyl-ethyl ketone and acetonitrile. Thesesolvents will merely be used for diluting the products to be polymerizedor cross-linked (to make them less viscous, especially when dealing witha prepolymer). They will be eliminated by drying after polymerization orcross-linking. Non-volatile solvents may also be mentioned. Anon-volatile solvent is also used for diluting the products that areintended to be polymerized or cross-linked, and to dissolve the saltA⁺X⁻ of the invention used as photoinitiator, however, it will remain inthe material formed and will thus act as a plasticizing agent. By way ofexample, propylene carbonate, γ-butyrolactone, ether-esters of mono-,di-, tri-ethylene or propylene glycols, ether alcohol of mono-, di-,tri-ethylene or propylene glycols, plasticizing agents such as phthalicacid esters or citric acid esters may be mentioned.

According to another embodiment of the invention, there is used assolvent or diluent a compound which is reactive towards polymerization,which has a low molecular weight and low viscosity and which will actsimultaneously as a polymerizable monomer and as solvent or diluent formore viscous monomers or prepolymers used jointly. After the reaction,these monomers which have been used as solvents will be part of themacromolecular network finally obtained, their integration being greaterwhen dealing with bi-functional monomers. The material obtained afterirradiation is now free of products having a low molecular weight and anappreciable vapour tension, or susceptible to contaminate objects withwhich the polymer is in contact. By way of example, a reactive solventmay be selected from mono- and di-vinyl ethers of mono-, di-, tri-,tetra-ethylene and propylene glycols, N-methylpyrolidone,2-propenylether of propylene carbonate which is commercially availablefor example under the designation PEPC from ISP, New Jersey, UnitedStates.

To irradiate the reaction mixture, the irradiation may be selected fromultraviolet radiation, visible radiation, X-rays, γ rays and βradiation. When ultraviolet light is used as an actinic radiation, itmay be advantageous to add to the photoinitiators of the inventionphotosensitizers intended to permit an efficient photolysis withwavelengths less energetic than those corresponding to a maximum ofabsorption of the photoinitiator, such as those emitted by industrialdevices (λ≈300 nm with mercury vapour lamps in particular). Suchadditives are known, and by way of non-limiting example, there may bementioned anthracene, diphenyl-9,10-anthracene, perylene, phenothiazine,tetracene, xanthone, thioxanthone, acetophenone, benzophenone,1,3,5-triaryl-2-pyrazolines and derivatives thereof, in particularderivatives which are substituted on the aromatic nuclei by alkyl, oxa-or aza-alkyl radicals enabling among others to change the; absorptionwavelength. Isopropylthioxantone is a preferred example ofphotosensitizer when an iodonium salt according to the invention is usedas a photoinitiator.

Among the various types of radiation mentioned, ultraviolet radiation isparticularly preferred. On the one hand, it is easier to use than theother radiations mentioned above. On the other hand, photoinitiators arein general directly sensitive to UV rays and photosensitizers especiallysince the difference of energy (δλ) is lower.

The ionic compounds of the invention may also be used in associationwith initiators of radical types which are produced thermally or by theaction of actinic radiation. It is thus possible to polymerize orcross-link mixtures of monomers or prepolymers containing functions inwhich the modes of polymerization are different, for example monomers orprepolymers which polymerize by free radical reaction and monomers orprepolymers which polymerize by cationic polymerization. Thispossibility is particularly advantageous for providing interpenetratednetworks having different physical properties from those which would beobtained by a mere mixture of polymers originating from correspondingmonomers. The vinyl ethers are not or are very little active by radicalinitiation. It is therefore possible, in a reaction mixture containing aphotoinitiator according to the invention, a free radical initiator, atleast one monomer of vinyl ether type and at least one monomercomprising non-activated double bonds such as those of the allyl groups,to carry out a separate polymerization of each type of monomer. On theother hand, it is known that monomers which are deficient in electrons,such as esters or amides of fumaric acid, maleic acid, acrylic ormethacrylic acid, itaconic acid, acrylonitrile, methacrylonitrile,maleimides and derivatives thereof, are formed in the presence ofelectron enriched vinyl ethers, charge transfer complexes which givealternating polymers 1:1 by free radical initiation. An initial excessof vinyl monomers with respect to this stoichiometry enablespreservation of polymerizable functions by pure cationic initiation.Triggering of the activity of a mixture of free radical initiator andcationic initiator according to the invention may be carried outsimultaneously for the two reactants in the case for example ofisolation with actinic radiation of a wavelength in which thephotoinitiators of the invention and the free radical initiatorsselected are active, for example λ=250 nm. By way of example ofinitiators, the following commercial products may be mentioned: Irgacure184®, Irgacure 651®, Irgacure 261®, Quantacure DMB®, Quantacure ITX®.

It may also be advantageous to use the two types of polymerization in asequential manner to form first prepolymers which are easy to produceand in which hardening, adhesiveness, solubility as well ascross-linking degree may be is modified by initiating the activity ofthe cationic initiator. For example, a mixture of a thermo-dissociablefree radical initiator and a cationic photoinitiator according to theinvention enables to provide sequential polymerization andcross-linkings, first under the action of heat, then under the action ofactinic radiation. In a similar manner, if a free radical initiator anda cationic photoinitiator according to the invention are selected, thefirst being photosensitive to longer wavelengths than the ones whichinitiate the photoinitiator according to the invention, there isobtained a cross-linking in two controllable steps. Free radicalinitiators may for example be Irgacure 651®, enabling initiation freeradical polymerizations at wavelengths of 365 nm.

It is also an object of the invention to use ionic compounds of theinvention for reactions of chemical amplification of photoresists formicrolithography. During such a use, a film of a material comprising apolymer and an ionic compound of the invention is subject toirradiation. The irradiation causes the formation of the acid byreplacement of the cation M with a proton, which catalyzes thedecomposition or transformation of the polymer. After decomposition ortransformation of the polymer on the parts of the film which have beenirradiated, the formed monomers or the polymer which has been convertedare eliminated and what remains is an image of the non-exposed parts.For this particular application, it is advantageous to use a compound ofthe invention which is in the form of a polymer consisting essentiallyof styrenyl recurring units having an ionic substituentR_(F)—SO_(x)—N⁻—. These compounds enable to produce, after photolysis,products which are non-volatile, and therefore non-odorous when dealingwith sulfides. Among the polymers which may thus be modified in thepresence of a compound of the invention, there may be mentioned forexample polymers containing ester groups or tertioalkyl arylethergroups, for example poly(phthaldehydes), polymers of bisphenol A and adiacid, polytertiobutoxycarbonyl oxy-styrene, polytertiobutoxy-α-methylstyrene, polyditertiobutylfumarate-co-allyltrimethylsilane andpolyacrylates of a tertiary alcohol, in particular tertiobutylpolyacrylate. Other polymers are described in J. V. Crivello et al,Chemistry of Materials 8, 376-381, (1996).

The ionic compounds of the present invention, which have a high thermalstability, have numerous advantages with respect to the known salts ofthe prior art. They have initiation and propagation speeds which arecomparable or higher than those obtained by means of coordination anionsof the type PF₆ ⁻, AsF₆ ⁻ and especially SbF₆ ⁻. In addition, thecoefficient of diffusion of the anion R_(F)—SO_(x)—N⁻— is higher thanthe one of hexafluorometallate anions or tetrafluoroborate anions orphenylborate anions. These properties are explained by thedelocalization of the negative charge and the flexibility of the anionaround the bond S—N.

In the compounds of the present invention, the pairs of ions have a veryhigh dissociation, which enables the expression of the intrinsiccatalyst properties of the cation M^(m+), in which the active orbits areeasily exposed to the substrates of the reaction, especially in variousmedia. Most of the important reactions of organic chemistry may thus becarried out under easy conditions, with excellent yields, and facilitatethe separation of the catalyst from the reaction mixture. The appearanceof asymmetric induction by the use of an ionic compound according to theinvention which carries a chiral group is particularly important becauseof its generality and its ease of application. It should be noted thatthe chiral perfluorinated molecules [R_(F)SO₂—N—SO₂R_(F)]⁻, 1/mM^(m+)are unknown and would only present a negligible optical activity becauseof the low polarizable character of the perfluorinated groups.Consequently, it is another object of the present invention to usecompounds of the invention as catalysts in Friedel and Craft reactions,Diels and Alder reactions, aldolization reactions, additions of Michael,allylation reactions, reactions of pinacolic coupling, reactions ofglycosilation, reactions of openings of oxetane cycles, reactions ofmethathesis of alcenes, polymerization of the Ziegler-Natta type,polymerizations of the type methathesis by opening of the cycle andpolymerizations of the type methathesis of acyclic dienes. The preferredionic compounds of the invention for use as catalyst in the reactionsmentioned above are those in which the cation is selected from lithium,magnesium, copper, zinc, tin, trivalent metals, including rare earths,platinoids, their organometallic couples, in particular metallocenes.

The compounds of the invention may also be used as a solvent forcarrying out chemical, photochemical, electrochemical,photoelectrochemical reactions. For this particular use, ionic compoundsin which the cation is an imidazolium, a triazolium, a pydridinium or a4-dimethylamino-pyridinium are preferred, said cation optionallycarrying a substituent on the carbon atoms of the cycle. The compoundsbeing used in liquid form, those which have a melting point lower than150° C., more particularly lower than 100° C. are particularlypreferred.

The inventors have also found that the anionic charge carried by thegroup R_(F)—SO_(x)—N⁻Z exerts a stabilizing effect on electronicconductors of the conjugated polymer type, and that the use of acompound in which the substituent Z comprises a long alkyl chain wouldcause these polymers to be soluble in the usual organic solvents, evenin doped state. Grafting of these charges on the polymer itself givespolymers in which the global charge is cationic, which are soluble inorganic solvents and provide, in addition to their stability, propertiesof anti-corrosiveness towards metals, such as aluminum and ferrousmetals. It is also an object of the present invention to provideelectronically-conductive materials comprising an ionic compound of thepresent invention in which the cationic part is a polycation consistingof a “p” doped conjugated polymer. The preferred ionic compounds forthis application are those in which the substituent Z contains at leastone alkyl chain having from 6 to 20 carbon atoms. By way of example, thecompounds in which Z is R_(D)Y—, R_(D) being an alkyl radical, may bementioned. There may also be mentioned compounds in which R_(F) isR_(A)CF₂—, R_(A)CF₂CF₂—, R_(A)CF₂CF(CF₃)— or CF₃C(R_(A))F— in whichR_(A)— represents an alkyl radical. Additionally, compounds in which Zrepresents an aromatic nucleus carrying an alkyl radical may also bementioned.

Coloring materials of cationic type (cyanines) are used more and morefrequently as sensitizers of photographic films, for the optical storingof information (optical disks which are accessible in writing), forlasers. The tendency of these conjugated molecules to be stacked overone another when they are in solid phases limits their use, because ofthe variations of the optical properties with respect to the isolatedmolecule. The use of ionic compounds of the invention for themanufacture of cationic coloring materials in which the counter ions,eventually fixed to this same molecule, correspond to the functions ofthe invention, enables to reduce the phenomenons of aggregation,including in solid polymer matrices, and to stabilize these coloringmaterials. It is another object of the invention to provide acomposition of colouring material, characterized in that it contains anionic compound according to the invention. The particularly preferredionic compounds of this application are those in which the negativecharge(s) of the ionic group R_(F)—SO_(x)—N⁻-Z are either fixed to themolecule of the colouring material or they constitute the counter-ion ofthe positive charges of the colouring material. By way of example ofsuch compounds, the following compounds may be mentioned:

The present invention is illustrated by the following examples, however,it is not limited thereto.

Examples 1 to 7 describe the preparation of some compounds used asreactants for the synthesis of the ionic compounds of the presentinvention. Examples 8 to 78 illustrate the preparation of compoundsaccording to the invention and their uses.

EXAMPLE 1 Trifluoromethanesulfonamide

To a suspension under strong stirring of 140.53 g (1.8 moles) ofammonium carbamate H₂NCO₂NH₄ (commercially available from Aldrich) in 1l of dichloromethane at 0° C., there is added drop-wise during 2 hours282.13 g (1 mole) of trifluoromethanesulfonic anhydride (CF₃SO₂)₂O(commercially available from Aldrich) diluted in 250 ml ofdichloromethane. Carbon dioxide evolved according to the followingreaction:(CF₃SO₂)₂O+1.5H₂NCO₂NH₄→CF₃SO₃ ⁻NH₄ ⁺+CF₃SO₂NH⁻NH₄ ⁺1.5CO₂

After 3 hours at 0° C., the reaction is continued for 24 hours at roomtemperature, and dichloromethane was evaporated and the product wasreclaimed with 400 ml of water. The addition of 250 ml of a solution ofhydrochloric acid 4 M has permitted release oftrifluoromethanesulfonamide CF₃SO₂NH₂ which was extracted with threefractions of 200 ml of ether. After drying the ether phase (600 ml) withmagnesium sulfate, the product was recovered after evaporation of etherand purified by sublimation under secondary vacuum at 60° C. There isobtained 137.16 g of trifluoromethanesulfonamide CF₃SO₂NH₂ (92% yield)having a purifity characterized by a proton and fluorine RMN higher than99%.

The corresponding sodium salt was prepared by reactingtrifluorormethanesulfonamide with sodium carbonate Na₂CO₃ in water (20%in excess). After evaporation of water and drying, the product obtainedwas reclaimed in acetonitrile and the excess of carbonate was removed byfiltration. After evaporation of acetonitrile and drying, there isobtained a quantative amount of sodium salt oftrifluoromethanesulfonamide CF₃SO₂NHNa.

Microanalysis has given: H, 0.52 (0.59); C, 7.22 (7.02); N, 8.41 (8.19);F, 33.82 (33.32); Na, 13.21 (13.44); S, 18.65 (18.74).

The lithium salt CF₃SO₂NHLi and potassium salt CF₃SO₂NHK have beenobtained by a similar process, by replacing sodium carbonaterespectively with lithium carbonate and potassium carbonate.

EXAMPLE 2 Fluorosulfonamide

The compound was prepared under similar conditions to those described inExample 1, by replacing the trifluoromethanesulfonamide CF₃SO₂NH₂ by182.11 g (I mole) of fluorosulfonic anhydride (FSO₂)₂O (commerciallyavailable from SST Corporation) previously purified by vacuumdistillation. There is obtained 80.25 g of fluorosulfonamide FSO₂NH₂(81% yield), having a purity characterized by a proton and fluorine RMNhigher than 99%. The corresponding sodium salt was prepared by dosing anaqueous solution at 0° C. of fluorosulfonamide FSO₂NH₂ with a titratedsolution of sodium hydroxide until reaching the neutralization pointdetermined by pH-men. After lyophilization and drying under vacuumduring 24 hours, the sodium salt of fluorosulfonamide FSO₂NHNa wasrecovered quantitatively.

Microanalysis has given: H, 0.78 (0.83); N, 11.32 (11.57); F, 15.12(15.69); Na, 18.66 (18.99); S, 26.01 (26.48).

The salts of lithium FSO₂NHLi and of potassium FSO₂NHK have beenobtained by a similar process, by replacing sodium hydroxiderespectively by lithium hydroxide and potassium hydroxide.

EXAMPLE 3 Pentafluoroethanesulfonyl Chloride

In 600 ml of ether cooled to −78° C. under argon, 60 g (244 mmoles) ofpentafluoroethyl iodine C₂F₅I (commercially available from StremChemicals) were condensed. Under stirring, there is then added 153 ml ofa solution 1.6 M of methyllithium in ether (244 mmoles), (commerciallyavailable from Fluka). After 5 minutes, there was introduced ≈20 g (≈312mmoles) of sulfur dioxide SO₂ into the solution, the reaction wascontinued during 2 hours at −78° C. Then, the solution was allowed toreach room temperature during 2 hours, and after 1 hour at roomtemperature, the solvents were evaporated. After drying, 44.51 g oflithium pentafluoroethanesulfinate C₂F₅SO₂Li (96% yield) were recovered.

A flow of chlorine Cl₂ was then allowed to pass in 200 ml of watercontaining 28.5 g (150 mmoles) of lithium pentafluoroethanesulfinateC₂F₅SO₂Li. Rapidly, there appeared a second phase, denser than waterwhich was extracted with fractions of 25 ml of anhydrousdichloromethane. After drying the organic phase with magnesium sulfate,26.55 g of pentafluoroethanesulfonyl chloride C₂F₅SO₂Cl (81% yield) wererecovered by fractionate distillation. The product has a puritycharacterized by a fluorine RMN fluorine higher than 99%.

EXAMPLE 4 Perfluorobutanesulfonamide

To 30.21 g (100 mmoles) of perfluoro-1-butanesulfonyl fluoride C₄F₉SO₂F(commercially available from Aldrich) and 8.91 g (100 mmoles) of ethylcarbamate C₂H₅O₂CNH₂ in 100 ml of anhydrous tetrahydrofurane at 0° C.,there is added in portions 1.75 g (220 mmoles) of 95% lithium hydrideLiH at 95% (commercially available from Aldrich). After stirring for 72hours under argon, the reaction mixture was centrifuged and filtered toremove the precipitate of lithium fluoride LiF and the excess of lithiumhydride. The solvent was thereafter evaporated and the product obtainedwas reclaimed in 100 ml of water. After adding 3.5 g (200 mmoles) oflithium hydroxide monohydrate, the reaction mixture was heated to areflux overnight to hydrolyze the ester function. After cooling, thereaction in mixture was given a pH≈1 by addition of a solution ofhydrochloric acid 10 M in order to remove the carboxyl function which ispresent, and it was extracted with three fractions of 50 ml of etherafter 24 hours of stirring. After drying of the organic phase withmagnesium sulfate and evaporation, 27.2 g ofperfluoro-1-butanesulfonamide C₄F₉SO₂NH₂ (91% yield) having a puritycharacterized by a proton and fluorine RMN higher than 99%, wererecovered after drying under vacuum.

The corresponding sodium salt was prepared by reactingperfluoro-1-butanesulfonamide with sodium carbonate Na₂CO₃ in water (20%in excess). After evaporating water and drying, the product obtained wasreclaimed in tetrahydrofurane and the excess of carbonate was removed byfiltration. After evaporation of tetrahydrofurane and drying, the sodiumsalt of perfluoro-1-butanesulfonamide C₄F₉SO₂NHNa was obtainedquantitatively.

Microanalysis has given: H, 0.25 (0.31); C, 15.35 (14.96); N, 4.63(4.36); F, 54.1 (53.25); Na, 7.36 (7.16); S, 10.35 (9.98).

The lithium and potassium salts were obtained by a similar process, byreplacing lithium carbonate respectively with sodium carbonate andpotassium carbonate.

EXAMPLE 5 Pentafluoroethanesulfonamide

10.93 g of pentafluoroethanesulfonyl chloride C₂F₅SO₂Cl, prepared as inExample 3, were added slowly to 50 ml of a 1 M solution of sodiumbis(trimethylsilyl)amide ((CH₃)₃Si)₂NNa in tetrahydrofurane (50 mmoles,commercially available from Aldrich) at −20° C.

After 2 hours at −20° C., the solvent was evaporated and the product wasreclaimed in 50 ml of water, the pH was brought to ≈2 and the aqueousphase was extracted with two fractions of 20 ml of ether. After dryingthe organic phase with magnesium sulfate, the recovered product wassublimated under vacuum. After 24 hours, 6.17 g ofpentafluoroethanesulfonamide C₂F₅SO₂NH₂ (62% yield) having a puritycharacterized by a proton and fluorine RMN higher than 99% wererecovered on a cold finger.

The corresponding sodium salt was prepared by reactingperfluoroethanesulfonamide with sodium carbonate Na₂CO₃ in water (20% inexcess). After evaporating water and drying, the product obtained wasreclaimed in tetrahydrofurane and the excess of carbonate was removed byfiltration. After evaporating tetrahydrofurane and drying, the sodiumsalt of perfluoroethanesulfonamide C₂F₅SO₂NHNa was obtainedquantitatively.

Microanalysis has given: H, 0.42 (0.46); C, 10.35 (10.87); N, 6.73(6.34); F, 42.01 (42.97); Na, 10.89 (10.4); S, 14.25 (14.5).

Salts of lithium and potassium were obtained by a similar process, byreplacing sodium carbonate respectively with lithium and potassiumcarbonate.

EXAMPLE 6 Potassium Triflinate

To a suspension in 50 ml of anyhydrous acetonitrile at −18° C. of 22.64g (100 mmoles) of the bi-potassium salt of2,2-dimercapto-1,3,4-thiadiazole (commercially available from Aldrich),there is added 17.36 g (103 mmoles) of trifluoromethanesulfonyl chlorideCF₃SO₂Cl. After 48 hours while stirring at room temperature, thereaction mixture was filtered to remove potassium chloride and thepoly(2,2-dimercapto-1,3,4-thia-diazole) formed during the reactionaccording to the following reaction scheme:

After evaporating the solvent and drying under vacuum at roomtemperature during 24 hours, 16.3 g of potassium triflinate CF₃SO₂K (95%yield) were recovered with a purity characterized by a fluorine RMNhigher than 98%.

Microanalysis has given: C, 6.72 (6.98); F, 32.6 (33.11); S, 18.32(18.62); K, 22.29 (22.71).

EXAMPLE 7 3-sulfonyl-1,2,4-triazine Chloride

28.83 (300 mmoles) of 3-amino-1,2,4,-triazine (commercially availablefrom Aldrich) were added to a mixture under stirring of 100 ml ofconcentrated hydrochloric acid and 30 ml of glacial acetic acid. Thereaction mixture was brought to −10° C. and 22.42 g (325 mmoles) ofsodium nitrite NaNO₂ in 35 ml of water were added slowly. Thediazotation reaction was allowed to proceed for 1 hour. At the sametime, a flow of sulfur dioxide SO₂ was passed through a frit in 300 mlglacial acetic acid until saturation. Following this, 7.5 g of copperchloride (I) CuCl were added and the addition of sulfur dioxide wascontinued until the colour of the reaction mixture went fromyellow-green to blue-green. After having brought the temperature of thereaction mixture to lower than 10° C., the previously prepared diazoniumwas added during 30 min. A small amount of ether was added to decreasethe quantity of foam which is formed after each addition. After the endof diazonium addition, the reaction mixture was poured into 1 litre of amixture of water and ice (1:1). After melting of the ice, a yellow oilwas separated in a decanting flask, and the aqueous phase was extractedwith two fractions of 100 ml ether. After adding the ether phase to theoil which has been collected, the solution was washed with aconcentrated solution of sodium bicarbonate until reaching neutrality,and then with water, and finally it was dried with magnesium sulfate.After evaporation of the solvent, 35.1 g of 3-sulfonyl-1,2,4-triazine(65% yield) having a purity characterized by proton and fluorine RMNhigher than 98% were collected after vacuum distillation.

Microanalysis has given: C, 20.6 (20.1); H, 0.6 (1.1); N, 23.6 (23.4);S, 17.6 (17.9); Cl, 19.3 (19.7).

EXAMPLE 8 3-chloropropanesulfonyl(trifluoromethanesulfonyl)-imide

17.7 g (100 mmoles) of 3-chloropropanesulfonyl chloride Cl(CH₂)₃SO₂Cland 37.44 g (200 mmoles) of potassium trifluoromethanesulfonamideCF₃SO₂NHK were reacted at 0° C. in 50 ml of tetrahydrofurane anhydride.After 3 hours at 0° C., and 24 hours at room temperature,tetrahydrofurane was evaporated and the product was crystallized in 40ml of water, recovered by filtration and dried. There were obtained 23.6g of the potassium salt oftrifluoromethanesulfonyl(3-chloropropanesulfonyl)-imideCl(CH₂)₃SO₂NKSO₂CF₃ (72% yield) having a purity characterized by protonand fluorine RMN higher than 99%.

Microanalysis has given: H, 1.76 (1.85); C, 14.23 (14.66); N, 4.56(4.27); F, 17.78 (17.39); S, 19.09 (19.56); Cl, 10.28 (10.82); K, 11.45(11.93).

By a similar process, the potassium salt offluorosulfonyl(3-chloropropane-sulfonyl)imide (65% yield) was obtainedfrom the potassium salt of fluorosulfonamide obtained in Example 2 andthe potassium salt ofpentafluroethane-sulfonyl(3-chloropropanesulfonyl)imide (82% yield) wasobtained from the potassium salt of pentafluorosulfonamide obtained inExample 5.

Lithium salts were obtained in quantitative yields by treatment of thepotassium salts in anhydrous tetrahydrofurane with a stoichiometricquantity of anhydrous lithium chloride, filtration of the reactionmedium, evaporation of the solvent and drying under vacuum.

These three salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly (ethyleneoxide). In this latter solvent at a concentration O/K of 14/1, they havean ionic conductivity greater than 10⁻³ S·cm⁻¹ at a temperature of 100°C.

These salts may be easily grafted on different substrates including asite which is sufficiently nucleophilic such as an alcoholate, an amideor a methylide.

EXAMPLE 9 2,2,2-trifluoroethanesulfonyl(trifluoromethanesulfonyl)imide

To a solution in 30 ml of anhydrous acetonitrile at 0° C. of 9.13 g (50mmoles) of 2,2,2-trifluoroethanesulfonyl CF₃CH₂SO₂Cl (commerciallyavailable from Aldrich) and 7.45 g (50 mmoles) oftrifluoromethanesulfonamide CF₃SO₂NH₂, 7.91 g (100 mmoles) of anhydrouspyridine were added drop-wise. After 2 hours at 0° C., the reaction wascontinued during 48 hours at room temperature. The reaction mixture wasthen filtered to remove the pyridinium hydrochloride formed. Thereaction mixture was then stirred during 48 hours with 5.79 g (50mmoles) of lithium phosphate Li₃PO₄. After filtration, evaporation ofthe solvent and drying, 14.6 g of the lithium salt oftrifluoromethanesulfonyl(2,2,2-trifluoroethane-sulfonyl) imideCF₃CH₂SO₂NLiSO₂CF₃ (97% yield) were obtained.

Microanalysis has given: H, 0.72 (0.67); Li, 2.48 (2.3); C, 11.56(11.97); N, 4.88 (4.65); F, 38.02 (37.86); S, 21.56 (21.3).

This salt has a conductivity of 2.3×10⁻⁴ S·cm⁻¹ at 60° C. in poly(ethylene oxide) at a concentration of O/Li of 12/1.

It has a proton presenting an acid character enabling to give reactionsof nucleophilic substitution in the presence of a base with, forexample, alkyl or acid halides.

EXAMPLE 10 N-methyl-sulfonyl(trifluoromethanesulfonyl)imide

Under argon, there is added drop-wise during 2 hours 100 mil of a 2Msolution of methylamine CH₃NH₂ (200 mmoles), (commercially availablefrom Aldrich) in tetrahydrofurane to a solution, at −20° C. under strongstirring, of 13.5 g (100 mmoles) of sulfuryl chloride SO₂Cl₂ in 50 ml ofanhydrous dichloromethane. After 3 hours at −20° C., the reactionmixture was subjected to centrifugation to remove the precipitate ofmethylammonium hydrochloride CH₃NH₃ ⁺Cl⁻formed. After evaporation oftetrahydrofurane, the remaining liquid was distilled under vacuum. Thereare obtained 12.82 g of N-methyl-chlorosulfonamide ClSO₂NH(CH₃) (95%yield) having a purity characterized by a proton RMN higher than 98%.

6.48 g (50 mmoles) of N-methyl-chlorosulfonamide were then reacted in 30ml of anhydrous tetrahydrofurane with 7.45 g (50 mmoles) oftrifluoromethanesulfonamide, and with 11.22 g (100 mmoles) of1,4-diazabicyclo[2.2.2]octane (DABCO). After 48 hours, the reactionmixture was filtered to remove the DABCO hydrochloride precipitateformed. After evaporation of the solvent, the product obtained wasreclaimed in 20 ml of ethanol and 40.91 g (100 mmoles) of potassiumacetate were added. The precipitate was then formed. Afterrecrystallization, filtration and drying, 9.95 g of potassiumtrifluoromethanesulfonyl(N-methylsulfonyl)imide CF₃SO₂NKSO₂NH(CH₃) (71%yield) were recovered, in which the purity characterized by proton andfluorine RMN is higher than 98%.

Microanalysis has given: H, 1.31 (1.44); C, 8.38 (8.57); N, 9.85 (9.99);F, 20.89 (20.34); S, 22.35 (22.88); K, 13.52 (13.95).

By a similar process, the potassium salt oftrifluoromethanesulfonyl(N-ethyl-sulfonyl)imide was obtained fromethylamine and the potassium salt oftrifluoromethanesulfonyl(N-propyl-sulfonyl)imide was obtained frompropylamine.

The lithium salts were prepared quantitatively by ionic exchange betweenthe potassium salts and lithium chloride in anhydrous tetrahydrofurane.

These compounds have a labile proton permitting to give reactions ofnucleophilic substitution in the presence of a base with alkyl and acidhalides for example.

EXAMPLE 11 5-formyl-2-furanesulfonyl(trifluoromethanesulfonyl)imide

To 9.91 g (50 mmoles) of the sodium salt of 5-formyl-2-furanesulfonicacid (commercially available from Aldrich) in 30 ml of anhydrousdimethylformamide at 0° C., 6.35 g (50 mmoles) of oxalyl chlorideClCOCOCl in solution in 20 ml of anhydrous dichloromethane were addedslowly, then, after 2 hours at 0° C., 18.72 g (100 mmoles) of thepotassium salt of trifluoromethanesulfonamide CF₃SO₂NHK were added. Thisreaction was continued for 48 hours at room temperature, and the solventwas evaporated and the product obtained was crystallized in 40 ml ofwater. After filtration and drying, 10.88 g of the potassium salt oftrifluoromethanesulfonyl(5-formyl-2-furanesulfonyl)imide (63% yield)having a purity determined by fluorine and proton RMN higher than 99%were recovered.

Microanalysis has given: H, 1.01 (0.88); C, 20.55 (20.87); N, 4.15(4.06); F, 16.91 (16.51); S, 18.17 (18.57); K, 11.76 (11.32).

By the same process, the potassium salt offluorosulfonyl(5-formyl-2-furane-sulfonyl)imide was obtained.

The aldehyde function enables grafting of this salt on substratescontaining a group capable of reacting with this function, for example,an amino group or a double bond.

EXAMPLE 12 Allylsulfonyl(trifluoromethanesulfonyl)imide

To 14.41 g (100 mmoles) of the sodium salt of 2-propene-sulfonicCH₂═CHCH₂SO₃Na in suspension in 60 ml of anhydrous acetonitrile at −20°C., 11.9 g (100 mmoles) of thionyl chloride SOCl₂ diluted in 20 ml ofbenzene were added drop-wise during 2 hours. The mixture was allowed tostand overnight at −20° C., and it was centrifuged to remove sodiumchloride formed and the solvents were evaporated by means of a rotaryevaporator provided with a membrane pump. The liquid obtained was thendistilled under vacuum in a short column to give 10.97 g of2-propene-sulfonyl CH₂═CHCH₂SO₂Cl (78% yield) characterized by a protonRMN. 7.03 g (50 mmoles) of this compound were then reacted with 18.72 g(100 mmoles) of potassium trifluoro-methanesulfonamide CF₃SO₂NHK in 60ml of an anhydrous acetonitrile at 0° C. during 2 hours, followed by areaction period at room temperature for 24 hours. After evaporation ofthe solvent, the product was recrystallized in 20 ml of water. Afterfiltration and drying, 17.22 g of the potassium salt oftrifluoromethane-sulfonyl(2-propenesulfonyl)imide CH₂=CHCH₂SO₂NKSO₂CF₃(66% yield) having a purity characterized by a proton and fluorine RMNhigher than 98%.

Microanalysis has given: H, 1.68 (1.73); C, 16.22 (16.49); N, 4.6(4.81); F, 19.12 (19.57); S, 22.29 (22.01); K, 13.23 (13.42).

According to the same process, the potassium salt ofpentafluoroethanesulfonyl(2-propene-sulfonyl)imide (69% yield) wasobtained from the potassium salt of pentafluoroethanesulfonamideobtained in Example 5.

These salts have the characteristic of homo-or copolymerizing by apolymerization which is initiated by free radical polymerization or bymeans of an olefin polymerization catalyst of the Ziegler-Natta type,such as a zircanocene, and more generally, they are characterized bybeing able to undergo chemical reactions inherent to ethylenic bonds.

EXAMPLE 13 3,4-epoxypropane-1-sulfonyl(trifluoromethanesulfonyl)imide

To 11.65 g (40 mmoles) of the potassium salt oftrifluoromethanesulfonyl(2-propenesulfonyl)imide, obtained in Example12, in 100 ml of water, there were added 6.9 g (40 mmoles) of3-chloroperoxybenzoic acid obtained according to the procedure describedby Schwartz & Blumbergs (J. Org. Chem., (1964), 1976). After 1 hour ofstrong stirring, the solvent was evaporated and the residue wasrecrystallized in 15 ml ethanol. After filtration and drying, 7.5 g ofthe potassium salt of2,3-epoxy-propane-1-sulfonyl(trifluoromethanesulfonyl)imide (61% yield)having a purity characterized by proton and fluorine RMN higher than 98%were recovered.

Microanalysis has given: H, 1.84 (1.64); C, 15.2 (15.63); N, 4.99(4.56); F, 18.01 (18.55); S, 20.15 (20.87); K, 12.01 (12.72).

According to the same procedure, there is obtained the potassium salt ofa 2,3-epoxypropane-1-sulfonyl(pentafluoroethanesulfonyl)imide from thepotassium salt of pentafluoroethanesulfonyl(2-propene-sulfonyl)imideobtained in Example 12.

Lithium salts were obtained by treating potassium salts in anhydroustetrahydrofurane with the stoichiometric quantity of anhydrous lithiumchloride, filtration of the reaction mixture, evaporation of the solventand drying under vacuum.

These salts may be homo- or copolymerized by means of a polymerizationinitiated by anionic or cationic means. More generally, they may undergochemical reactions which are inherent to oxetanes.

The homopolymer of2,3-epoxypropane-1-sulfonyl(trifluoromethanesulfonyl)imide was preparedby polymerization in tetrahydrofurane which was initiated by anionicpolymerization with potassium tert-butoxide, then the polysalt oflithium was prepared by ionic exchange with anhydrous lithium chloride.The latter has a conductivity in a gelled medium (21% by weight ofpolyacrylonitrile, 38% ethylene carbonate, 33% propylene carbonate, 8%homopolymer) of 1.1×10⁻³ S·cm⁻¹ at 30° C. The cationic transport numberof this electrolyte is 0.82. Moreover, this homopolymer is soluble inmost of the usual organic solvents (tetrahydrofurane, acetonitrile,dimethylformamide, ethyl acetate, glymes, . . . ) and in aproticsolvating polymers.

EXAMPLE 14 Vinylsulfonyl(trifluoromethanesulfonyl)imide

To a solution at 0° C. and under argon of 8.15 g (50 mmoles) of2-chloro-1-ethane-sulfonyl chloride ClCH₂CH₂SO₂Cl (commerciallyavailable from Aldrich) and 7.45 g (50 mmoles) oftrifluoromethanesulfonamide CF₃SO₂NH₂ in 25 ml of anhydroustetrahydrofurane, there is added drop-wise during 30 min, a solution of16.83 g (150 mmoles) of DABCO diluted in 25 ml of anhydroustetrahydrofurane. After the end of the addition of the base, thereaction is continued during 2 hours at 0° C., and then for 24 hours atroom temperature. The reaction mixture was then filtered to remove theDABCO hydrochloride formed. Then, 2.12 g of anhydrous lithium chloride(50 mmoles) were added, the reaction mixture was stirred during 24hours, and it is again filtered to remove the DABCO hydrochlorideformed. After evaporation of tetrahydrofurane and drying, 11.89 g of thelithium salt of trifluoromethanesulfonyl(vinylsulfonyl)imideCH₂═CHSO₂NLiSO₂CF₃ (98% yield) were recovered having a purity which ischaracterized by a proton and fluorine RMN higher than 98%.

Microanalysis has given: H, 1.28 (1.23); Li, 2.78 (2.83); C, 14.91(14.7); N, 5.82 (5.71); F, 22.5 (23.25); S, 25.8 (26.16).

According to the same process, the lithium salt ofperfluorobutanesulfonyl)vinyl-sulfonyl)imide (99% yield) was obtainedfrom the perfluorobutanesulfonamide obtained in Example 4.

These salts may be homo- or copolymerized by a polymerization which isinitiated by free radical polymerization. More generally, they mayundergo chemical reactions which are inherent to activated vinyl bonds,in particular additions of Michael, with for example an alcoholate.

EXAMPLE 15 7,8-octene-3,6-oxa-1-sulfonyl(trifluoromethanesulfonyl)imide

To 2.2 g (25 mmoles) of ethylene glycol vinyl ether CH₂═CHO(CH₂)₂OH in60 ml of anhydrous dimethylformamide, there is added 6.13 g (25 mmoles)of the lithium salt of vinylsulfonyl(trifluoromethanesulfonyl)imide,obtained in Example 14, 5.87 g of anhydrous potassium carbonate K₂CO₃(42.5 mmoles) and 330 mg (1.25 mmoles) of a crown ether, 18-Crown-6(acting as complexing agent of the potassium cation). The reactionmixture was then stirred under argon at 85° C. After 48 hours, thereaction mixture was filtered on a fritted glass of porosity No 3, andthe solvent was evaporated under reduced pressure. After drying, thecompound was recrystallized in 10 ml of water containing 1.86 g (25mmoles) of anhydrous potassium chloride KCl. After filtration anddrying, 5.66 g of the potassium salt of7,8-octene-3,6-oxa-1-sulfonyl(trifluoromethane-sulfonyl)imide (62%yield) having a purity characterized by a proton and fluorine RMN higherthan 98% was recovered.

Microanalysis has given: H, 3.12 (3.03); C, 23.26 (23.01); N, 3.77(3.83); F, 15.89 (15.6); S, 17.12 (17.55); K, 10.23 (10.7).

There is obtained a quantitative yield of the lithium salt by treatmentof the potassium salt in anhydrous tetrahydrofurane with thestoichiometric quantity of anhydrous lithium chloride, filtration of thereaction mixture, evaporation of the solvent and drying under vacuum.

This salt may be homopolymerized by cationic polymerization. It may alsobe copolymerized by cationic polymerization, optionally bypolymerization which is alternated with an unsaturated monomer. Moregenerally, it may undergo chemical reactions which are characteristic ofalkyl vinyl ethers.

The homopolymer prepared by polymerization in anhydrous acetonitrileinitiated by cationic polymerization withbis(trifluoromethanesulfonyl)imide has a conductivity at a concentrationof 0.8 M in a mixture of dimethylcarbonate and ethylene carbonate (2:1)of 6×10⁻³ S·cm⁻¹ at 30° C. Moreover, this homopolymer is soluble in mostof the known organic solvents (tetrahydrofurane, acetonitrile,dimethylformamide, ethyl acetate, glymes, . . . ) and in the aproticsolvating polymers such as poly (ethylene oxide).

EXAMPLE 16 4-styrenesulfonyl(trifluoromethanesulfonyl)imide

In 100 ml of anhydrous tetrahydrofurane under argon at 0° C., 20.27 g(10 mmoles) of 4-styrenesulfonyl chloride CH₂═CHC₆H₄SO₂Cl (commerciallyavailable from Monomer-Polymer & Dajac Laboratories) were reacted with14.91 g (10 mmoles) of trifluoromethane-sulfonamide CF₃SO₂NH₂ and 22.44g (20 mmoles) of (DABCO). After 2 hours at 0° C. and 48 hours at roomtemperature, the solution was filtered to remove the DABCO hydrochlorideformed, and it was thereafter treated with 424 mg (10 mmoles) ofanhydrous lithium chloride, which is stored and weighed in a glove box.Immediately, a precipitate of DABCO hydrochloride was formed and thereaction mixture was then again filtered after stirring for 6 hours.After evaporation and drying under vacuum, during 24 hours at roomtemperature, 31.16 g of the lithium salt oftrifluoromethane-sulfonyl(4-styrenesulfonyl)imide were recovered whichhave a purity characterized by a proton and fluorine RMN higher than97%.

Microanalysis has given: H, 2.4 (2.2); Li, 2.56 (2.16); C, 33.15(33.65); N, 4.79 (4.36); F, 17.14 (17.74); S, 19.51 (19.96).

According to the same process, lithium salts offluorosulfonyl(4-styrenesulfonyl)-imide (98% yield) were prepared fromthe fluorosulfonamide obtained in Example 2, ofpentafluoroethanesulfonyl(4-styrenesulfonyl)imide (97% yield) from thepentafluoroethanesulfonamide obtained in Example 5 and ofperfluorobutanesulfonyl(4-styrenesulfonyl)imide (99% yield) from theperfluorobutanesulfonamide obtained in Example 4.

These salts may be homo- or copolymerized by polymerization initiated byanionic, cationic and more particularly free radical means. They mayalso be grafted on a polymer matrix such as vinylidene polyfluoride byirradiation.

The homopolymers obtained by free radical polymerization in deaeratedwater, initiated by cyanovaleric acid at 60° C. are soluble in the usualorganic solvents and in aprotic solvating polymers. In poly(ethyleneoxide) at a concentration O/Li of 16/1, these salts have a conductivity≈6×10⁴ S·cm⁻¹ at 100° C. Moreover, in a concentrated solution in acetone(≈1 M as lithium cation), these homopolymers may be used as catalysts inDiels-Alder reactions, and in this way they act as chemicalmicro-reactors.

EXAMPLE 175-(4-methylene-1,3-dioxolane)-2-furanesulfonyl(trifluoromethanesulfonyl)imide

5.18 g (15 mmoles) of the potassium salt oftrifluoromethanesulfonyl(5-formyl-2-furanesulfonyl)imide, 1.66 g (15mmoles) of 3-chloro-1,2-propanediol ClCH₂CH(OH)CH₂(OH) (commerciallyavailable from Aldrich) and ≈1 mg of p-toluenesulfonic acid monohydratewere mixed in 30 ml of toluene. An azeotropic distillation was thencarried out until the appearance of water in the Dean-Stark ceased to beobserved. After evaporation of the solvent, the product obtained wasrecrystallized in 10 ml of water. After filtration and drying, 5.13 g ofthe potassium salt of5-(4-methylene-1,3-dioxolane)-2-furanesulfonyl(trifluoromethane-sulfonyl)imide(82% yield) were recovered, and this product had a purity determined byproton and fluorine RMN higher than 98%.

Microanalysis has given: C, 26.65 (26.93); H, 1.89 (1.76); N, 3.99(3.49); S, 15.28 (15.98); F, 13.8 (14.2); K, 9.41 (9.74).

A quantitative yield of the lithium salts was obtained by treatment ofthe potassium salt in anhydrous tetrahydrofurane with a stoichiometricquantity of anhydrous lithium chloride, filtration of the reactionmixture, evaporation of the solvent and drying under vacuum.

This salt may be homo- or copolymerized by a polymerization initiated bycationic or free radical means. The homopolymer of this salt wasobtained by photopolymerization, which is initiated by cationic meansthrough irradiation of tris(4-methylphenyl)sulfoniumhexafluoroantimonate with a U.V. lamp during 10 min at 36° C. It has aconductivity at a concentration of 0.5 M in tetraethylsulfamide(C₂H₅)₂NSO₂N(C₂H₅) of 4×10³ S·cm⁻¹ at 20° C.

EXAMPLE 181-acryloyl-2,2,2-trifluoroethanesulfonyl-(trifluoromethanesulfonyl)imide

By operating in a glove box under argon, 7.53 g (25 mmoles) of thelithium salt oftrifluoromethanesulfonyl(2,2,2-trifluoro-ethanesulfonyl)imideCF₃CH₂SO₂NLiSO₂CF₃, prepared as in Example 9, were solubilized in 15 mlof anhydrous tetrahydrofurane. After adjusting the temperature of thissolution to −20° C., 50 ml of a 1 M solution (25 mmoles) intetrahydrofurane of sodium bis(trimethylsilyl)amide ((CH₃)₃Si)₂NNa(commercially available from Aldrich) were added. After 15 min, there isslowly added 2.26 g (25 mmoles) of acryloyl chloride CH₂═CHCOClpreviously purified by distillation under vacuum. The reaction wascontinued during 2 hours at −20° C., and the reaction mixture wasfiltered to remove the precipitate of sodium chloride. The solvent wasthen evaporated and there is obtained after drying under vacuum at roomtemperature 8.7 g (98% yield) of the lithium salt oftrifluoromethanesulfonyl(1-acryloyl-2,2,2-trifluoroethanesulfonyl)imideCH₂=CHCOCH(CF₃)SO₂NLiSO₂CF₃ having a purity characterized by a protonand fluorine RMN higher than 98%.

Microanalysis has given: H, 1.26 (1.14); Li, 1.69 (1.95); C, 20.06(20.29); N, 3.79 (3.94); F, 32.33 (32.1); S, 18.26 (18.05).

This salt may be homo- or copolymerized by photopolymerization in thepresence of a photo-sensitizer.

There is prepared a mixture containing this salt (16 weight %), apoly(ethylene glycol) dimethacrylate having a molar weight of 600 g/mole(81 weight % commercially available from Aldrich), particles of silicahaving a specific surface of 300 m²/g (3 weight %, Aerosil, commerciallyavailable from Degussa AG) and xanthone. This solution was depositedwith a reel on a glass plate covered with a layer of tungsten trioxideWO₃ and a conductive sub-layer of tin oxide. There is obtained amembrane which is optically transparent in the visible range and whichadheres on the support by photopolymerization initiated by irradiationby means of U.V. lamp during 10 min at 32° C. Then, an electrochromesystem was prepared by assembling in a glove box a counter-electrodeconsisting of the deposit on a glass plate of a layer of hydrogenatediridium oxide H_(x)IrO₂ and a sub-layer of tin oxide. This electrochromehas given a variation of the optical absorption from 80% (discolouredstate) to 30% (coloured state) and good performances in cycling is thuspossible to produce a number of cycles of coloring/discoloring greaterthan 20,000.

EXAMPLE 19 3-maleimidopropanesulfonyl(trifluoromethanesulfonyl)imide

To a solution of 2.43 g of maleimide (25 mmoles) in 20 ml of anhydroustetrahydrofurane there were added by portions 215 mg of lithium hydrideLiH (27 mmoles). After 1 hour, a potassium salt oftrifluoromethanesulfonyl(3-chloropropane-sulfonyl)imide prepared as inExample 8 was added to the filtered solution. The reaction was continuedduring 24 hours at 60° C., and the reaction mixture was filtered toremove the potassium chloride KCl precipitate, the solvent wasevaporated and the product was dried. There is thus obtained 8.37 g (94%yield) of the lithium salt oftrifluoromethanesulfonyl(3-maleimido-propanesulfonyl)imide(—COCH═CHCO—)N(CH₂)₃SO₂NLiSO₂CF₃ having a purity characterized by aproton and fluorine RMN≈96%.

Microanalysis has given: H, 2.15 (2.26); Li, 2.15 (1.95); C, 26.72(26.97); N, 7.66 (7.86); F, 16.54 (16); S, 18.25 (18).

According to the same process, the lithium salt ofpentafluoroethanesulfonyl(3-maleimido-propanesulfonyl)imide (98% yield)was obtained from the potassium salt ofpentafluoroethane-sulfonyl(3-chloropropanesulfonyl)imide obtained inExample 8.

These salts may be homopolymerized by free radical or anionicpolymerization or can be copolymerized by anionic or free radicalpolymerization optionally by polymerization alternated with an electrondonor monomer (N-vinyl-2-pyrrolidone, N-vinyl formamide, vinyl ether, .. . ).

The homopolymer prepared by polymerization in anhydrous tetrahydrofuraneat −78° C., initiated by anionic polymerization with sec-butyllithium,is soluble in the usual organic solvents (tetrahydrofurane,acetonitrile, dimethylformamide, ethyl acetate, glymes, . . . ) and inaprotic solvating polymers such as poly (ethylene oxide).

EXAMPLE 202-(triethoxysilyl)ethanesulfonyl(trifluoromethanesulfonyl)imide

In a Parr chemical reactor, there is introduced a solution of 9.36 g (50mmoles) of the potassium salt of trifluoromethanesulfonamide CF₃SO₂NHKand 264 mg of a potassium cation complexing crown ether, 18-Crown-6, in60 ml of anhydrous acetonitrile. After closing the reactor, flushingwith argon was carried out during 15 min before isolating it. There werethen introduced 6.41 g (50 mmoles) of sulfur dioxide SO₂ (commerciallyavailable from Fluka) and, after 10 min, 9.52 g (50 mmoles) ofvinyltriethoxysilane (commercially available from Fluka) in solution in20 ml of anhydrous acetonitrile. After 6 hours at room temperature, thetemperature of the reactor was raised to 40° C. and was kept at thattemperature during 48 hours, and the solvent was evaporated. Afterdrying under vacuum, the product was stored under argon. A quantitativeyield of the potassium salt oftrifluoromethanesulfonyl(2-triethoxysilyl)ethane-sulfonyl)imide having apurity characterized by a fluorine and proton RMN higher than 99% wasrecovered.

Microanalysis has given: H, 4.79 (4.34); K, 8.27 (8.85); C, 24.99(24.48); N, 3.89 (3.17); F, 12.15 (12.91); Si, 6.75 (6.36); S, 14.33(14.52).

The lithium salt was obtained by ionic exchange with lithium chloride intetrahydrofurane.

The corresponding acid was obtained by co-crushing in an agate mortar,under a glove box, the potassium salt with three equivalents (150mmoles) of anhydrous ammonium hydrogen sulfate HSO₄NH₄ (commerciallyavailable from Aldrich). Then, by secondary sublimation under vacuum at40° C., trifluoromethanesulfonyl(2-(triethoxy-silyl)ethanesulfonyl)imidewas recovered after 24 hours on a cold finger at a temperature of −40°C.

These salts enable formation of organosilicon networks by a mechanism ofhydrolysis-polycondensation. They also permits seeding of glass basematerials (fibre, glazing, . . . ) in order to modify their surface.

In addition, homopolymers or copolymers may be obtained with variousalkoxysilanes in a protic medium, optionally in the presence of acatalyst (acid, base, fluoride, . . . ).

A copolymer was prepared by polycondensation of the potassium salt oftrifluoromethanesulfonyl-(2-triethoxysilyl)ethanesulfonyl)imide withO-[20(trimethoxysilyl)ethyl]-O′-methylpolyethylene glycol of molecularweight 5,000 (commercially available from Shearwaters Polymers) (5:1molar) in a water/methanol mixture by using as catalysttrifluoromethanesulfonyl(2-(triethoxysilyl)ethane-sulfonyl)imide. Aftera few hours, the solution was concentrated. Then, a pad of activatedcharcoal, previously de-gassed, having a specific surface of 1,500 m²/g(commercially available from Actitex), was impregnated with the viscousliquid obtained. After drying, this operation was repeated to improvethe impregnation. After having maintained the impregnated pad during 1week in a dryer at 50° C., two buttons having a diameter of 2 cm werecut out by stamping. A sheet of cigarette paper (commercially availablefrom Bolloré Technologies) was then impregnated with a viscous liquididentical to the one used to impregnate the carbon pad. This sheet wasplaced between the two buttons of impregnated carbon pad which were usedas carbon electrodes. After 1 week in a dryer at 50° C., and 2 daysunder vacuum at 60° C., there is obtained a “all-solid” electrochemicalsupercapacitance. This supercapacitance has given the followingperformances at 40° C.: a density of energy of 15 Wh/l (or a capacity of96 F/g of carbon for an electrode), a maximum power of 700 V/kg and goodresults in cycling (more than 10,000 cycles of charge/discharge between0 and 2V). Such a supercapacitance is particularly interesting in thefield of electronics because of the absence of volatile liquids.

A solution of the potassium salt oftrifluoromethanesulfonyl-(2-(triethoxysilyl)ethanesulfonyl)imide withO-[2-(triethoxysilyl)ethyl]-O′-methyl-polyethylene glycol having amolecular weight of 5,000 (commercially available from ShearwatersPolymers) (3:1 molar) was prepared in a mixture of water/methanol. Aglass plate pickled with nitric acid and dried at 100° C. was thereaftersoaked in the solution for a few minutes. After rincing with methanoland drying, a surface conductivity of 3×10⁻⁵ S (square) was measuredwhich is sufficient to give antistatic properties to the surface of theglass.

EXAMPLE 21bis[3-(trimethoxysilyl)propyl]aminosulfonyl(trifluoro-methanesulfonyl)imide

5.96 g (40 mmoles) of trifluoromethane-sulfonamide CF₃SO₂NH₂ and 8.97 g(40 mmoles) of DABCO in 60 ml of anhydrous dichloromethane were cooledat −30° C. 5.4 g (40 mmoles) of sulfuryl chloride SO₂Cl₂ and 12.54 g (40mmoles) of bis[3-(trimethoxysilyl)propyl]amine of formula[(CH₃₀)₃Si(CH₂)₃]₂NH were then added drop-wise. The mixture was stirredduring 4 hours at −30° C., and for 24 hours at room temperature. 1.7 gof anhydrous lithium chloride LiCl were then added, the reaction mixturewas stirred during 24 hours, and filtered to removed the precipitate ofDABCO hydrochloride. After evaporation of the solvent and drying undervacuum, 21.88 g (98% yield) of the lithium salt ofbis[3-(trimethoxysilyl)propyl]aminosulfonyl(trifluoro-methanesulfonyl)having a purity characterized by a fluorine and proton RMN higher than98% were recovered.

Microanalysis has given: H, 5.32 (5.41); Li, 1.56 (1.24); C, 27.66(27.95); N, 5.22 (5.01); F, 10.56 (10.2); Si, 10.26 (10.06); S, 11.67(11.48).

This compound has properties analogous to those of the compound ofExample 20 and may be used for the same applications.

This compound was polycondensed in a water/methanol mixture, utilizing adrop of concentrated hydrochloric acid as catalyst. After a few hours,the solvents were evaporated and the viscous liquid obtained was pouredon a Teflon® plate. After one week in a dryer at 50° C., the materialobtained was dried under vacuum at 100° C. during 48 hours, and crushedunder argon until obtaining a particle size of the order of 1 micron. Acomposite electrolyte was then prepared by mixing this powder with poly(ethylene oxide) of molecular weight M_(W)=3.10⁵ in acetonitrile. Afterhaving poured this dispersion in a glass ring and having evaporated theacetonitrile, there is obtained a film of composite electrolyte having agood mechanical behaviour, a thickness of 220 μm. This electrolyte hasan ionic conductivity greater than 10⁻⁵ S¹·cm¹ at 60° C. The cationictransport number is 0.92.

EXAMPLE 22N-methyl-N-vinylester-sulfonyl(trifluoromethane-sulfonyl)imide

To 7.01 g (25 mmoles) of the potassium salt oftrifluoromethanesulfonyl(N-methylsulfonyl)imide CF₃SO₂NKSO₂NH(CH₃),prepared as in Example 10, in solution in 15 ml of anhydroustetrahydrofurane, there was slowly added under argon 25 ml of a 1 Msolution in tetrahydrofurane of potassium tert-butoxide (CH₃)₃COK (25mmoles, commercially available from Aldrich). After a few minutes, 2.66g (25 mmoles) of vinylchloroformate CH₂═CHO₂CCl (commercially availablefrom Lancaster), previously distilled under vacuum, were added. Thereaction is continued during 24 hours at room temperature. The reactionmixture was then filtered to remove the precipitate of potassiumchloride, the solvent was evaporated and the product was dried undervacuum. There is obtained 8.58 g (98% yield) of the potassium salt oftrifluoromethanesulfonyl-(N-methyl-N-vinylester-sulfonyl)imideCF₃SO₂NKSO₂N(CH₃)CO₂CH═CH₂.

Microanalysis has given: H, 1.56 (1.73); C, 17.56 (17.14); N, 8.37 (8);F, 17.01 (16.27); S, 18.56 (18.3); K, 11.46 (11.16).

The lithium salt was obtained with quantitative yield by treating thepotassium salt in anhydrous tetrahydrofurane with the stoichiometricquantity of anhydrous lithium chloride, filtration of the reactionmixture; evaporation of the solvent and drying under vacuum.

This salt may be homo- or copolymerized by means of a polymerizationinitiated by free radical.

There is produced a film of polymer electrolyte, having a thickness of30 μm, consisting of the lithium salt in solution in a poly (ethyleneoxide) matrix having ethylenic unsaturations, at a concentrationO/Li=26/1, and containing 1% by weight of cyanovaleric acid and 3% byweight of silica having a specific surface of 300 m²/g (Aerosil,commercially available from Degussa AG). This polymer was obtained bypolycondensation of polyethylene glycol of a molecular weight 1,000 with*3-chloro-2-chloromethyl-1-propene according to the procedure describedby Alloin & al. (J. Power Sources, (1995), 26, 34-39). On the otherhand, on a sheet of aluminum, a composite electrode having a thicknessof 90 μm containing 45% by volume of vanadium dioxide (V₂O₅), 5% byvolume of Kedenblack® K600 (commercially available from Akzo) as anadditive of electronic conduction, and 50% by volume of a polymerelectrolyte of the same composition as the one described above, wasprepared. In a glove box under argon, the film of polymer electrolytewas then deposited on the composite electrode, the film being coveredwith a film of lithium with a thickness of 30 μm, deposited on a sheetof aluminum. The temperature of the assembly was then adjusted to 60° C.during 24 hours by applying a slight pressure. There is thus obtained anelectrochemical generator with fixed anions, the lithium saltco-cross-linking with the double bonds of the polymer matrix. Thisgenerator gave a satisfactory result during cycling at 70° C. (72% ofthe capacity after 10 cycles at the 500th cycle of charge/discharge).Performances during calls for power were also improved.

EXAMPLE 23 4-perfluorovinyloxyphenylsulfonyl(pentafluorosulfonyl)imide

Under argon, at 9.95 g (50 mmoles) of pentafluoroethanesulfonamideC₂F₅SO₂NH₂ in solution in 40 ml of anhydrous tetrahydrofurane at −20°C., 10 ml of a 10 M solution of butyllithium in hexane C₄H₉Li (100mmoles) were slowly added. After 2 hours, 14.63 g of(3-(1,1,2,2-tetrafluoroethoxy)benzene sulfonyl chloride (50 mmoles),prepared from (3-(1,1,2,2-tetrafluoroethoxy)aniline according to thegeneral process described in Example 7, were added. The reaction wascontinued during 24 hours at −20° C., and 50 ml of a 10 M solution ofbutyllithium in hexane C₄H₉Li (50 mmoles) were added. After 2 hours, thetemperature was allowed to rise to ambient and the solvents wereevaporated. The product was reclaimed in 30 ml of ethanol andrecrystallized after addition of 4.91 g (50 mmoles) of potassium acetateCH₃COOK. After filtration and drying, 17.25 g of the potassium salt ofpentafluoroethanesulfonyl(3-(1,1,2-tri-fluorovinyloxy)benzenesulfonyl)imide(78% yield) having a purity characterized by a proton and fluorinehigher than 98% were obtained.

Microanalysis has given: H, 1.1 (0.85); C, 25.62 (25.37); N, 2.69(2.96); F, 33.1 (32.11); S, 13.16 (13.55); K, 8.95 (8.26).

According to the same process, the potassium salt oftrifluoromethane-sulfonyl(3-(1,1,2-trifluorovinyloxy)benzenesulfonyl)imide(98% yield) was obtained from trifluoromethanesulfonamide.

The corresponding acids were obtained by ether extraction of acidifiedaqueous solutions of various potassium salts. Lithium salts wereobtained by treating different acids with lithium carbonate Li₂CO₃.

These salts may be homo- or copolymerized by free radical initiatedpolymerization.

A porous textile made from GORE-TEX® with a thickness of 100 μm,commercialized by Gore, was impregnated with a concentrated solution oftrifluoromethane-sulfonyl(3-(1,1,2-trifluorovinyloxy)-benzene-sulfonyl)imideoxide in dichloromethane containing cyanovaleric acid as polymerizationinitiator. After evaporation of the solvent, the acid washomopolymerized within the textile matrix by increasing the temperatureof the product under argon to 60° C. during 24 hours. The membrane thusobtained was used as electrolyte in a test cell of a polymer electrolytebattery with combustible hydrogen/oxygen. The life span obtained withthis membrane was longer than 1,000 hours, with good power performances.This membrane may also be used for the Friedel-Crafts heterogeneouscatalysis of the acylation reaction of toluene with benzoyl chloride.

EXAMPLE 24 2,2-fluorovinylsulfonyl(trifluoromethane-sulfonyl)imide

Under argon, to a solution of 6.02 g (20 mmoles) of the lithium salt oftrifluoromethane-sulfonyl(2,2,2-trifluoroethanesulfonyl)imide obtainedin Example 9, in 40 ml of anhydrous tetrahydrofurane at −20° C., therewas slowly added 10 ml of a 2 M solution of butyllithium in cyclohexaneC₄H₉Li (20 mmoles, commercially available from Aldrich). After 2 hoursat −20° C., the reaction mixture was centrifuged to remove theprecipitate of lithium fluoride which has appeared during the reaction.After evaporation of the solvents and drying, the lithium salt of2,2-fluorovinylsulfonyl(trifluoro-methanesulfonyl)imide having a puritydetermined by a proton and fluorine RMN higher than 99% was recoveredwith quantitative yield.

Microanalysis has given: H, 0.47 (0.36); Li, 2.71 (2.47); C, 12.51(12.82); N, 4.72 (4.98); F, 33.54 (33.79); S, 22.65 (22.81).

This salt may be homo- or copolymerized by a free radical initiatedpolymerization.

The homopolymer prepared by polymerization in anhydrous tetrahydrofuraneat 66° C., initiated by free radical with1,1′-azobis(cyclohexane-carbonitrile), is soluble in the usual organicsolvents (tetrahydrofurane, acetonitrile, dimethylformamide, ethylacetate, glymes, . . . ) and in aprotic solvating polymers such as poly(ethylene oxide). In an aqueous solution at 25° C., it has aconductivity of 9.3×10⁻³ S·cm⁻¹ at a concentration of 0.5 M. It givesantistatic properties to coatings containing same.

EXAMPLE 25 Dimethylaminosulfonyl(trifluoromethanesulfonyl)imide

To a solution at 0° C. and under argon of 14.36 g (100 mmoles) ofsulfamoyl chloride (CH₃)₂NSO₂Cl (commercially available from Aldrich)and 14.91 g of trifluoromethanesulfonamide CF₃SO₂NH₂ (100 mmoles) in 60ml of anhydrous tetrahydrofurane, there is added 22.44 g (200 mmoles) ofDABCO in solution in 20 ml of anhydrous tetrahydrofurane at 0° C. After2 hours at 0° C., the reaction was continued during 24 hours at roomtemperature. The precipitate of DABCO hydrochloride was removed byfiltering on a fritted glass of porosity No. 4. Then, there is added4.24 g (100 mmoles) of anhydrous lithium chloride, the reaction mixturewas stirred during 24 hours, and it was again filtered to remove theDABCO hydrochloride formed. After evaporation of tetrahydrofurane anddrying, 25.17 g (96% yield) of the lithium salt oftrifluoromethanesulfonyl-(dimethylaminosulfonyl)imide Me₂NSO₂NLiSO₂CF₃having a purity characterized by a fluorine and proton RMN higher than99% was recovered.

Microanalysis has given: H, 2.34 (2.31); Li, 2.52 (2.65); C, 13.96(13.65); N, 10.75 (10.69); F, 21.25 (21.74); S, 24.35 (24.46).

According to the same process, the lithium salt ofpentafluoroethanesulfonyl(dimethyl-aminosulfonyl)imide (98% yield) wasprepared from the pentafluoroethanesulfonamide obtained in Example 5.

These salts have an excellent solubility in the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly (ethyleneoxide). In this latter solvent, at a concentration O/Li=12/1, thelithium salt of0.48-trifluoromethanesulfonyl(dimethylaminosulfonyl)imide has a anionicconductivity of 1.2×10⁻⁴ S·cm⁻¹ at 60° C. The concentrated solutions ofthe salts in acetone may be utilized as catalyst for Diels-Alderreactions.

A lithium-polymer generator was produced by utilizing a metallic lithiumanode, an electrolyte made of a terpolymer of ethylene oxide,allylglycidylether and methylglycidylether containing the lithium saltof trifluoromethanesulfonyl(dimethylaminosulfonyl)imide at aconcentration O/Li=20/1, and a composite cathode based on vanadium oxide(40% by volume), carbon black (5% by volume) and an electrolyteidentical to the one described above (50% by volume). This generator hasgiven a cycling profile at 60° C. which is equivalent to the oneobtained by utilizing one of the more currently known salts for thisapplication, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI).

EXAMPLE 26 Dimethylaminosulfonyl(trifluoromethanesulfonyl)imide

To a solution kept at 0° C. and under argon containing 14.36 g (100mmoles) of sulfamoyl chloride (CH₃)₂NSO₂Cl (commercially available fromAldrich) and 14.91 g of trifluoromethanesulfonamide CF₃SO₂NH₂ (100mmoles) in 60 ml of anhydrous tetrahydrofurane, there is added 22.44 g(200 mmoles) of DABCO in solution in 20 ml of anhydrous tetrahydrofuraneat 0° C. After 2 hours at 0° C., the reaction was continued during 24hours at room temperature. The precipitate of DABCO hydrochloride wasremoved by filtration on a fritted glass of porosity No. 4. Afterevaporation of tetrahydrofurane and drying, the product was solubilizedin 25 ml of ethanol. There is then added 9.81 g (100 mmoles) ofpotassium acetate CH₃COOK, then the precipitate obtained with ethanolreflux was recrystallized. After cooling, filtration and drying, 24.13 g(82% yield) of the potassium salt oftrifluoromethanesulfonyl-(dimethylaminosulfonyl)imide Me₂NSO₂NKSO₂CF₃having a purity characterized by a fluorine and proton RMN higher than99% were recovered.

Microanalysis has given: H, 2.21 (2.05); C, 12.56 (12.24); N, 9.78(9.52); F, 19.89 (19.37); S, 21.56 (21.79); K, 13.11(13.28).

By the same process, the potassium salt ofperfluorobutanesulfonyl(dimethyl-aminosulfonyl)imide (85% yield) wasobtained from perfluorobutanesulfonamide obtained in Example 4.

The potassium salt oftrifluoromethanesulfonyl)-dimethylaminosulfonyl)imide has a meltingpoint of 188° C. It has a conductivity in poly(ethylene oxide) at aconcentration O/K=12/1 at 60° C. of 5.10⁻⁴ S·cm⁻¹.

The conductivity of a mixture of the potassium salt and the lithium,salt obtained in Example 25, in a ratio K/Li=2/1 and for a totalconcentration in alkaline cation O/(Li+K)=14/1 in poly (ethylene oxide)was also determined. This conductivity is identical to the onedetermined for the potassium salt alone, which indicates a mechanism ofvehicular transport of lithium in the, complex electrolyte by the anionswhich thus travel in the form of an anionic complex, which has littleinteraction with the basic solvent. This type of conductivity is veryfavourable to the operation of lithium generators and more particularlypolymer electrolyte generators, since performances during calls forpower are improved.

EXAMPLE 27 Dimethylaminosulfonyl(trifluoromethanesulfonyl)imide of2,2′-azobis (2-methylpropionamidine)

5.89 g (20 mmoles) of the potassium salt oftrifluoromethanesulfonyl(dimethylaminosulfonyl)imide Me₂NSO₂NKSO₂CF₃,prepared according to Example 26, were placed in solution in 10 ml ofwater. Under stirring, 2.71 g of 2,2′-azobis(2-methylpropionamidine)hydrochloride [═NC(CH₃)₂C(═NH)NH₂]₂.2 HCl (10 mmoles, commerciallyavailable from Aldrich) in solution in 10 ml of water were added. Thereis immediately formed a precipitate which was collected by filtration.After drying under vacuum at room temperature, 4.36 (96% yield) of2,2′-azobis (2-methylpropionamidine)dimethylaminosulfonyl(trifluoromethanesulfonyl)imide[═NC(CH₃)₂C(═NH)NH₂]₂.2 Me₂NSO₂NHSO₂CF₃ were recovered.

This salt is a free radical polymerization initiator which is soluble inmost usual organic solvents (tetrahydrofurane, acetonitrile,dimethylformamide, ethyl acetate, glymes, . . . ) and in aproticsolvating polymers, contrary to 2,2′-azobis(2-methylpropionamidine)hydrochloride.

An acetonitrile solution of 1 part of this initiator and 100 parts of apolymer containing ethylenic unsaturations was prepared. This polymerwas obtained by polycondensation of polyethylene glycol of molecularweight 1,000 with 3-chloro-2-chloromethyl-2-propene according to theprocedure described by Alloin et al. (Solid States Ionics, (1993), 60,3). The viscous solution obtained was poured on a polypropylene film(PP). After evaporation of the solvent, the polymer film of a thicknessof 110 μm on PP was stored for one week in a glove box under argon fordrying. Cross-linking was then initiated by raising the temperature ofthe film to 60° C. After 1 night, there is obtained a film having goodmechanical properties and a low rate of substances that can be extracted(lower than 1%). The solubility of the initiator used in the polymermatrix therefore enables to give an efficient and homogeneouscross-linking. Moreover, this initiator is not volatile, contrary forexample to 2,2′-azobisisobutyronitrile, and the quantity added may beoptimized to the best for each type of polymerization.

EXAMPLE 28 Dialkylaminosulfonyl(trifluoromethanesulfonyl)imide

15.85 g (200 mmoles) of dibutylamine (C₄H₉)₂NH in solution in 50 ml ofanhydrous tetrahydrofurane were treated with 27.83 g (200 mmoles) ofsulfur trioxide complexed with trimethylamine (CH₃)₃N—SO₃. Afterstirring for 24 hours at room temperature, the solvent was evaporatedand the product was reclaimed in 40 ml of methanol. After having added19.63 g (200 mmoles) of potassium acetate CH₃CO₂K and re-crystallizingthe precipitate obtained, there is recovered after filtration and drying32.66 g of the potassium salt of sulfonic acid of dibutylamine(C₄H₉)₂NSO₃K (66% yield). To 12.37 g of this salt (50 mmoles) in 50 mlof tetrahydrofurane at 0° C., 6.35 g (50 mmoles) of oxalyl chlorideClCOCOCl, and after 2 hours at 0° C., 18.72 g (100 mmoles) of thepotassium salt of trifluoromethanesulfonamide CF₃SO₂NHK were addedslowly. The reaction was continued for 48 hours at room temperature, andthe solvent was evaporated and the product obtained was recrystallizedin 50 ml of water. After filtration and drying, 14.38 g of the potassiumsalt of trifluoromethanesulfonyl(dibutyl-aminosulfonyl)imide(C₄H₉)₂NSO₂NKSO₂CF₃ (76% yield) having a purity characterized by aproton and fluorine RMN higher than 99% were recovered.

Microanalysis has given: H, 4.65 (4.79); C, 28.23 (28.56); N, 7.1 (7.4);F, 15.52 (15.06); S, 16.45 (16.94); K, 10.52 (10.33).

By a similar process, potassium salts of amides carrying a diethylsubstituent (C₂H₅)₂NSO₂NKSO₂CF₃ (66% yield) were prepared fromdiethylamine, and amides carrying a di-2-ethylhexyl substituent[C₄H₉—CH(C₂H₅)—CH₂]₂NSO₂NKSO₂CF₃ (70% yield) was prepared fromdi-2-ethylhexylamine, with purities characterized by proton and fluorineRMN higher than 98%.

By a similar process, the different potassium salts offluorosulfonyl(dialkylaminosulfonyl)imides were prepared from thefluorosulfonamide obtained in Example 2, the potassium salts ofpentafluoroethanesulfonyl(dialkyl-aminosulfonyl)imides were preparedfrom the pentafluoroethanesulfonamide obtained in Examiner 5 andpotassium salts of perfluorobutanesulfonyl(dialkylaminosulfonyl)imides(C₄H₉)₂NSO₂NKSO₂C₄F₉ were prepared from the perfluorobutanesulfonamideobtained in Example 4.

By ionic exchange in acetone between the potassium salt oftrifluoromethane-sulfonyl(di-2-ethylhexylaminosulfonyl)imide with aninfrared coloring material of the cyanine family,3,3′-diethylthiatricarbocyanine (commercially available from Aldrich)followed by re-precipitation in water, it was possible to obtain afterfiltration and drying the compound 3,3′-diethylthiatricarbocyanine ofdi-2-ethylhexylaminosulfonyl(trifluoro-methanesulfonyl)imide.

This salt is very soluble in low polar solvents such as dichloromethaneor methylene chloride as well as in polymer matrices with low polaritysuch as methyl polymethacrylate.

It was also possible to note a very distinct decrease of the aggregationof cationic colouring materials between one another because of the“plasticizing” character of the groups di-2-ethylhexylamino, which is anadvantage insofar as the phenomenon of aggregation brings a winding ofthe optical absorption bands which is prejudicial to the precision ofthe operation of systems utilizing these colouring materials, inparticular optical disks for storing information.

EXAMPLE 29 Dimethylaminosulfonyl(trifluoromethanesulfonyl)imideimidazolium

14.71 g (50 mmoles) of the potassium salt oftrifluoromethanesulfonyl(dimethylaminosulfonyl)imide (CH₃)₂NSO₂NKSO₂CF₃is prepared according to Example 26, were co-crushed in an agate mortarunder a glove box with 17.27 g (150 mmoles) of ammonium hydrogenosulfateHSO₄NH₄ (commercially available from Aldrich). By sublimation undersecondary vacuum at 80° C., there is recovered on a cold finger after 24hours 11.2 g (87% yield) oftrifluoromethanesulfonyl(dimethylaminosulfonyl)imide (CH₃)₂NSO₂NHSO₂CF₃having a purity characterized by a fluorine and proton RMN higher than99%.

To a solution in 15 ml of ether containing 1.36 g of imidazole (20mmoles), there is added 5.12 g of this acid (20 mmoles), and after 24hours under stirring, a precipitate formed is recovered by filtration ona fritted glass of porosity No. 3. After drying, a quantitative amountof the imidazolium salt oftrifluoromethanesulfonyl-(dimethylaminosulfonyl)imide was recovered.

A crushing under a glove box of a molar mixture of 7 imidazoles for 2imidazolium salts has enabled to give a compound having a meltingtemperature lower than ambient. This molten salt has an elevatedprotonic conductivity which is higher than 10⁻³ S·cm⁻¹ at 60° C. It ispossible to obtain a polymer electrolyte, which is an anhydrous protonicconductor by adding poly (ethylene oxide), preferably of high molecularweight or which can later be cross-linked, to the molten salt withoutdetrimentally affecting the conductivity. These polymer electrolytes areparticularly interesting for the preparation of systems for themodulation of light such as electrochrome glass panes includingelectrochrome systems containing coloring materials.

There is obtained a membrane which is optically transparent in visiblelight and having a good mechanical behaviour by utilizing a polymerelectrolyte made of 80% by weight of molten salt and 0.20% by weight ofpoly (ethylene oxide) of molecular weight M_(W)=5.10⁶. There was thenproduced an electrochrome system under glove box by utilizing thiselectrolyte enclosed between a first electrode consisting of the depositon a glass plate of a layer of hydrogenated iridium oxide H_(x)IrO₂ anda conductive sub-layer of tin oxide and a second electrode consisting ofa layer of tungsten trioxide H_(x)IrO₂ and a conductive sub-layer of tinoxide. This electrochrome led to a variation of the optical absorptionfrom 80% (discolored state) to 30% (colored state) and good performancesin cycling (more than 20,000 cycles of coloring/discoloring).

An electrochrome was also produced by dissolving two complimentarycoloring materials in such a molten salt: in a glove box, 1.62 g (5mmoles) of the imidazolium salt oftrifluoromethanesulfonyl(dimethylaminosulfonyl)imide and 1.02 g ofimidazole (15 mmoles) were crushed together. Then, to the molten salt,there was added 16.5 mg (50 μmoles) of green leucomalachite (colorlessreduced state) and 29.5 mg (50 μmoles) of the salt of3-(4,5-dimethyl-thiazolyl-2-yl)-2,5-diphenyl-2H-tetrazolium (MTT) andtrifluoromethanesulfonyl(dimethyl-aminosulfonyl)imide (colorlessoxidized state, obtained by ionic exchange in water starting from thebromide.). Then, there was added 5% by weight of poly (ethylene oxide)of molecular weight M_(W)=3.105. The salt obtained was placed between 2glass plates covered with a conductive layer of tin oxide (SnO₂). Afterpressing under vacuum to homogenize the deposit and sealing it to makeit impervious, there is obtained a coloring material base electrochromesystem. After having sealed the product obtained to make it impervious,a potential of 1,300 mV was applied on the outside by means of apotentiostat. The system then became colored, and the oxidized form ofgreen malachite and the reduced form of MTT each has an intenseabsorption band in the visible range. By applying a potential of −500mV, a relatively rapid discoloring of the system (lower than 60 s) wasnoted. Such an electrochrome system is easy to prepare, even for systemsof large sizes (higher than m²) which utilize glass or a suitablytreated polymer as conductive transparent electrode. Moreover, theenergy which is necessary to maintain coloration is relatively low,lower than 1 W/m².

EXAMPLE 30 EXAMPLE 30Dimethylaminosulfonyl(trifluoromethanesulfonyl)imide

To 2.56 g of trifluoromethanesulfonyl(dimethyl-aminosulfonyl)imide(CH₃)₂NSO₂NHSO₂CF₃ (10 mmoles.), obtained as in Example 29, in solutionin 10 ml of water, there is added 763 mg (1.67 mmoles) of anhydrouslanthanum carbonate La₂(CO₃)₂. After stirring overnight, water wasevaporated and the lanthanum salt oftrifluoromethanesulfonyl(dimethylaminosulfonyl)-imideCH₃)₂NSO₂NSO₂CF_(3]3)La was recovered in quantitative yield afterdrying.

This salt is highly soluble in the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) It is also capable of interaction with solvents with lowpolarities such as dichloromethane, which interaction is better thanthat of the lanthanum salt of bis(trifluoromethane-sulfonyl)imide. Itmay be used as a catalyst in Diels-Alder reactions.

EXAMPLE 31 Dialkylaminosulfonyl(trifluoromethanesulfonyl)imide

To 3.78 g (10 mmoles) of the potassium salt oftrifluoromethanesulfonyl(dimethylaminosulfonyl)imide (CH₃)₂NSO₂NKSO₂CF₃,obtained in Example 26, in solution in 10 ml of anhydrous nitromethane,there is added in a glove box, 1.17 g of nitrosonium tetra-fluoroborateNOBF₄ (10 mmoles, commercially available from Aldrich). After 1 hour,the reaction mixture was filtered to remove the insoluble potassiumtetrafluoroborate, and there is thus obtained a solution 1 M oftrifluoromethanesulfonyl-(dimethylaminosulfonyl)imide(CH₃)₂NSO₂N(NO)SO₂CF₃ in nitromethane.

By a similar process, a 1 M solution in nitromethane of the nitrosoniumsalt of trifluoromethanesulfonyl(dibutyl-aminosulfonyl)imide(C₄H₉)₂NSO₂N(NO)SO₂CF₃, was prepared from the potassium salt oftrifluoromethanesulfonyl-(dibutylaminosulfonyl)imide (obtained inExample 28) and another 1 M solution in nitromethane of the nitrosoniumsalt of trifluoromethane-sulfonyl(N,N-di-2-ethylhexylaminosulfonyl)imide(C₄H₉CH(C₂H₅)CH₂)₂N(NO)SO₂CF₃, was prepared from the potassium salt oftrifluoromethanesulfonyl-(N,N-di-2-ethylhexylaminosulfonyl)imide(obtained in Example 28).

These salts are particularly interesting for doping conjugated polymers(polythiophene, polypyrrole, . . . ) to which they give a notableelectronic conductivity.

Three deposits of stereoregular poly(3-hexyl-thiophene) (commerciallyavailable from Aldrich) were prepared on glass plates from a chloroformsolution. After drying, these deposits were doped with one of the saltsin solution in nitromethane. After doping, the threepoly(3-hexylthiophene) films had an electronic conductivity higher than1 S·cm⁻¹ independently of the doping salt. Stability in humid medium ofthe conductivity was improved with an increase of the length of thealkyl segments. These deposits are useful for preparing masks in thesemi-conductor industry.

EXAMPLE 32 Dialkylaminosulfonyl(trifluoromethanesulfonyl)imide

5.96 g (40 mmoles) of trifluoromethane-sulfonamide CF₃SO₂NH₂ and 9.9 mlof pyridine in 60 ml of anhydrous dichloromethane were cooled at −20° C.5.4 g (40 mmoles) of sulfuryl chloride SO₂Cl₂ diluted in 10 ml ofanhydrous dichloromethane and 8.1 g (80 mmoles) of dipropylamine(C₃H₇)₂NH were then added drop-wise. The mixture was stirred for 1 hourat −20° C. and during 24 hours at room temperature. The reaction mixturewas then filtered, and the solvent was evaporated. The product which wasrecovered was reclaimed in 50 ml of water, acidified at a pH ≈2 with asolution of hydrochloric acid 4 M, the aqueous phase was extracted twicewith 20 ml of ether, the organic phase was dried with magnesium sulfate,and ether was evaporated. After sublimation of the compound obtainedunder secondary vacuum at 40° C., 10 g oftrifluoromethanesulfonyl(dipropylaminosulfonyl)imide (80% yield) havinga purity characterized by a fluorine and proton RMN higher than 98% wererecovered.

The lithium salt was prepared by pH-metry dosing the acid in solution inwater with a titrated solution of lithium hydroxide. After evaporatingwater and drying under vacuum at 60° C. during 24 hours, the lithiumsalt of trifluoromethanesulfonyl(dipropylaminosulfonyl)-imide(C₃H₇)₂NSO₂NLiSO₂CF₃ was recovered in quantitative yield in the form ofa white powder.

Microanalysis has given: H, 4.33 (4.43); Li, 2.01 (2.18); C, 26.59(26.42); N, 8.69 (8.8); F, 17.33 (17.91); S 20.46 (20.15).

According to the same process, the lithium salt oftrifluoromethanesulfonyl(N-methyl-N-ethylaminosulfonyl)imideCH₃(C₂H₅)NSO₂NLiSO₂CF₃ was prepared by the same process and it has apurity determined by a proton and fluorine RMN higher than 99% with ayield of 76%.

These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly (ethyleneoxide).

The lithium salt of trifluoromethanesulfonyl(dipropylaminosulfonyl)imidehas a conductivity of 1.4×10⁻⁴ S·cm¹ in poly (ethylene oxide) at aconcentration O/Li=12/1 and the cationic transport number is 0.42.

EXAMPLE 33 3-(trifluoromethyl)phenyl(trifluoromethanesulfonyl)amide

To 48.34 g of 3-(trifluoromethyl)aniline (300 mmoles) in 250 ml ofanhydrous dichloromethane at 0° C., there is added drop-wise during 2hours, 28.21 g of trifluoromethanesulfonic anhydride (CF₃SO₂)20 (100mmoles) diluted in 100 ml of anhydrous dichloromethane, and the reactionwas continued during 24 hours at room temperature. After evaporation ofdichloromethane, the product obtained was reclaimed in 300 ml of water,then acidified with 25 ml of a 4 M solution of hydrochloric acid. Theaqueous solution was then extracted by means of three fractions of 50 mlof ether, the organic phases were combined and dried with magnesiumsulfate. After evaporation of ether and drying, the product obtained waspurified by sublimation under secondary vacuum at 40° C. After 24 hours,25 g of trifluoromethanesulfonyl(3-(trifluoromethyl)phenyl)amidem-CF₃C₆H₄NHSO₂CF₃ (85% yield) were recovered on a cold finger in theform of a white solid crystalline product having a purity characterizedby a fluorine and proton RMN higher than 99%.

Microanalysis has given: H, 1.65 (1.72); C, 32.53 (32.77); N, 4.62(4.78); F, 38.12 (38.88); S, 10.72 (10.94).

The lithium salt was prepared by treating the acid obtained with lithiumphosphate Li₃PO₄ during 48 hours in acetonitrile. After filtration ofthe reaction mixture, evaporation of the solvent and drying under vacuumat 60° C. during 24 hours, the lithium salt oftrifluoromethanesulfonyl(3-(trifuoromethyl)phenyl) amidem-CF₃C₆H₄NLiSO₂CF₃ was obtained in quantitative yield.

Sodium and potassium salts were obtained by a similar process, whilereplacing lithium phosphate respectively with sodium and potassiumphosphate.

In the same manner,trifluoromethanesulfonyl(3-5-bis(trifluoromethyl)-phenyl)amide (I) wasprepared from 3-5-bis(trifluoromethyl)aniline,trifluoromethanesulfonyl(4-tri-fluoromethoxy)phenyl)amide (II) wasprepared from trifluoromethanesulfonyl(4-trifluoromethoxy)aniline,trifluoromethanesulfonyl(4-aminopyridine)amide (III) was prepared from4-amino-pyridine and trifluoromethanesulfonyl(2,2,2-trifluoroethyl)amide(IV) was prepared from 2,2,2-trifluoroethylamine, as well ascorresponding lithium, sodium and potassium salts.

For all these salts, derivatives of the type fluorosulfonyl wereobtained by utilizing fluorosulfonic anhydride (FSO₂)₂O (commerciallyavailable from SST Corporation) instead of trifluoromethanesulfonicanhydride.

These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly (ethyleneoxide). They have an oxidation potential higher than 4 V towards alithium anode. The salts of lithium or potassium, or mixtures thereof,may therefore be used for preparing electrolytes (liquids, gels orpolymers) for lithium batteries which utilize a cathode material havinga potential of end of recharge lower than 4 V (TiS₂, V₂O₅, Fe(PO₄)₂).Tin salts (II) may be used for catalyzing aldolic condensations.

EXAMPLE 34 Trifluoro-methane-sulfonyl(2-trifluoromethyl-1,3,4-thiadiazole-5-amino)amide

By operating in a glove box under argon, to 16.91 g (100 mmoles) of2-amino-5-trifluoromethyl-1,3,4-thiadiazole (commercially available fromAldrich) in solution in 100 ml of anhydrous tetrahydrofurane at −30° C.,there is added drop-wise 100 ml of a 1 M solution of dibutylmagnesium(C₄H₉)₂Mg (100 mmoles, commercially available from Aldrich) in heptane.After 4 hours at −30° C., 16.85 g (100 mmoles) oftrifluoromethanesulfonyl chloride CF₃SO₂Cl were added slowly. Thereaction is continued during 2 hours at −30° C., then for 24 hours atroom temperature. The solvents were then evaporated, the product wasreclaimed in water and extracted with ether after acidifying the aqueoussolution. The compound obtained after evaporation of ether wassublimated under secondary vacuum at 40° C., and 25.73 g oftrifluoromethanesulfonyl(5-trifluoromethyl-1,3,4-thiadiazole)amide (86%yield) were thus recovered on a cold finger after 24 hours.

Microanalysis has given: H, 0.39 (0.33); C, 15.29 (15.95); N, 13.28(13.95); F, 38.3 (37.85); S, 20.62 (21.29).

The lithium salt was obtained by treating the acid with lithiumcarbonate Li₂CO₃ in water.

This salt is soluble in most usual organic solvents (tetrahydrofurane,acetonitrile, dimethylformamide, ethyl acetate, glymes, . . . ) and inaprotic solvating polymers such as poly (ethylene oxide).

This salt has an oxidation potential in a mixture of ethylene carbonateand dimethylcarbonate (2:1), at a concentration of 1 M, higher than 4Vtowards a lithium anode.

EXAMPLE 35 Trifluoro-methane-sulfonyl(2-trifluoromethyl-thiadiazole-5-aminosulfonyl)imide

First, 5-trifluoromethyl-2,3,4-thiadiazole-2-sulfonyl chloride wasprepared from 2-amino-trifluoromethyl-1,3,4-thiadiazole (commerciallyavailable from Aldrich), following the procedure described in Example 7.

Then, by a procedure similar to the one used in Example 25 for thesynthesis of the lithium salt ofdimethylaminosulfonyl(trifluoromethanesulfonyl)imide, the lithium saltoftrifluoromethanesulfonyl(5-trifluoromethyl-1,3,4-thiadiazole-5-sulfonyl)imidewas synthesized. The product obtained has a purity determined by protonand fluorine RMN higher than 98%.

Microanalysis has given: Li, 1.36 (1.9); C, 13.29 (12.9); N, 11.88(11.3); F, 31.4 (30.7); S, 26.46 (25.9).

This salt is soluble in most usual organic solvents (tetrahydrofurane,acetonitrile, dimethylformamide, ethyl acetate, glymes, . . . ) and inaprotic solvating polymers such as poly (ethylene oxide).

This salt has an oxidation potential, at a concentration of 0.5 M inacetonitrile, higher than 4.5 V towards a lithium anode. It may be usedfor Li-Ion batteries with liquid or gel electrolytes. Thus, a batterywas assembled by utilizing an anode consisting of coke carbon (80% byvolume) mixed with vinylidene polyfluoride (PVDF, commercially availablefrom Montedison) as binder (20% by volume), an electrolyte compound of amixture of ethylene carbonate and dimethylcarbonate (2:1), gelled withPVDF, containing this salt at a concentration of 1 M and a compositecathode consisting of carbon black (6% by volume), Li₂MnO₄ (75% byvolume) and PVDF as binder (20% by volume). This generator has givengood performances in cycling at 25° C. (1,000 cycles of charge/dischargebetween 2 and 4.7 V by maintaining about 50% of the capacity at thefirst cycle).

EXAMPLE 36Trifluoro-methane-sulfonyl(2-trifluoromethylthiadiazole-5-aminosulfonyl)amide

In 20 ml of anhydrous acetonitrile under stirring, 2.29 g (10 mmoles) oftrichloromelamine (commercially available from Fluka) were treated with5.16 g of potassium triflinate in the presence of 6.37 g of potassiumphosphate K₃PO₄ (30 mmoles). After 72 hours under stirring, the solventwas evaporated and the residue was recrystallized in 40 ml of water.After filtration and drying, 10.69 g (56% yield) of a potassium trisaltof tris-[1,3,5-trifluoromethanesulfonamide]-2,4,6-triazine with a puritydetermined by a proton and fluorine RMN higher than 99%.

Microanalysis has given: C, 11.52 (11.32); N, 13.61 (13.2); F, 26.99(26.86); S, 15.01 (15.11); K, 18.21 (18.43).

The trisalt of lithium was obtained by ionic exchange with lithiumchloride LiCl in tetrahydrofurane.

The lithium salt is soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly (ethyleneoxide). In this latter solvent containing the lithium salt at aconcentration O/Li=12/1, the cationic transport number is 0.52 at 60° C.

The tri-salt of tetrabutylammonium was obtained by treatment of thelithium tri-salt with tetrabutylammonium chloride (5% in excess) inwater. The precipitate obtained was thereafter recovered by extractionwith dichloromethane, the dichloromethane solution was washed withwater, and evaporated. The tri-salttris-[1,3,5-trifluoromethanesulfonamide]-2,4,6-triazinetri-tetrabutylammonium was recovered in quantitative yield. An additionof 3.5% by weight of this compound to a poly(acrylonitrile-co-butadiene)copolymer containing ≈20% by weight of acrylonitrile gives antistaticproperties to the copolymer.

EXAMPLE 37Trifluoromethanesulfonyl(1,1,1,3,3,3-hexafluoro-2-propanoxysulfonyl)imide

5.96 g (40 mmoles) of trifluoromethanesulfonamide CF₃SO₂NH₂ and 9.9 mlof pyridine in 60 ml of anhydrous dichloromethane were cooled to −15° C.5.4 g (40 mmoles) of sulfuryl chloride SO₂C12 diluted in 10 ml ofanhydrous dichloromethane were added drop-wise, and this was followed by6.72 g (40 mmoles) of 1,1,1,3,3,3-hexafluoro-2-propanol (CF₃)₂CHOH. Themixture was stirred for 1 hour at −15° C., and during 12 hours at roomtemperature. The reaction mixture was thereafter filtered, and thesolvent was evaporated. The product which was recovered was reclaimed in50 ml of water, acidified with 10 ml of a hydrochloric acid solution 4M; the aqueous phase was extracted twice with 20 ml of ether, theorganic phase was dried with magnesium sulfate and ether was evaporatedby means of a rotary evaporator. After sublimation under secondaryvacuum at 40° C. of the compound obtained, 13.9 g oftrifluoromethanesulfonyl(1,1,1,3,3,3-hexafluoro-2-propanoxysulfonyl)imide(92% yield) having a purity characterized by a fluorine and proton RMNhigher than 98% were recovered.

Microanalysis has given: H, 0.46 (0.53); C, 12.35 (12.67); N, 3.76(3.69); F, 44.3 (45.09); S, 16.23 (16.91).

An aqueous solution of the lithium salt was obtained by treating theacid with lithium carbonate Li₂CO₃ in water. Then, by addition of1-ethyl-3-methyl-1H-imidazolium chloride (10% in excess, commerciallyavailable from Aldrich), a liquid phase of higher density than water wasobtained. This phase was recovered by extraction with dichloromethane.After evaporation of dichloromethane and drying under vacuum at 40° C.of the liquid obtained, the molten salt oftrifluoromethanesulfonyl(1,1,1,3,3,3-hexafluoro-2-propanoxysulfonyl)imide1-ethyl-3-methyl-1H-imidazolium was recovered (91% yield).

This molten salt has a conductivity of 3.91×10⁻³ S·cm⁻¹ and a freezingpoint lower than −20° C. Its large range of redox stability enables itto be a particularly interesting electrolyte for electrochemicalgenerators such as lithium batteries, supercapacitances, systems formodulating light and photovoltaic cells.

An electrochemical photovoltaic cell was prepared by assembling a systemmade of two electrodes separated by a vacuum space 30 μm thick. Thefirst electrode was coated with a layer of nanoparticles of titaniumdioxide TiO₂ 0.25 μm thick on which the1,3-phenylsulfonamide-N,N′-trifluoro-methanesulfonyl rhodamine Bobtained in Example 25 was adsorbed as a sensitizer. The space betweenthe electrodes was filled with an electrolyte made of the molten salt inwhich 10% by weight of methylhexyl imidazolium and 10 mmoles of iodinewere solubilized. The short circuit current of this cell is 103 μA·cm⁻²and its voltage in open circuit was 552 mV.

EXAMPLE 38 Cyano(perfluorobutanesulfonyl)imide

To 5.16 g (60 mmoles) of cyanamide di-sodium (commercially availablefrom Aldrich) in 30 ml of dimethoxyethane at 0° C., there is added 15.1g of perfluorobutanesulfonyl fluoride (50 mmoles) at 0° C. After 3 hoursat 0° C., and 24 hours at room temperature, the reaction mixture wascentrifuged and filtered to remove the excess of cyanamide and thesodium fluoride formed. The product obtained was reclaimed in 20 ml ofmethanol after evaporation of dimethoxyethane, and 4.91 g of anhydrouspotassium acetate CH₃COOK (50 mmoles) were added. The precipitate whichwas formed is recrystallized, and recovered by filtration. After drying,12.5 g of potassium perfluorobutanesulfonyl (cyano)imide C₄F₉SO₂NKCN(69% yield) were obtained in the form of a white powder having a puritycharacterized by a fluorine and proton RMN higher than 97%.

Microanalysis has given: C, 16.18 (16.58); N, 7.23 (7.73); F, 47.98(47.21); S, 8.12 (8.85); K, 11.2 (10.79).

In the same manner, potassium salts of cyano(fluorosulfonyl)imide (I)were prepared from fluorosulfonyl chloride ClSO₂F,cyano(trifluoromethanesulfonyl)imide (II) was prepared fromtrifluoromethanesulfonyl chloride CF₃SO₂Cl andcyano(pentafluoroethanesulfonyl)imide (II) was prepared frompentafluoroethanesulfonyl chloride C₂F₅SO₂Cl.

The lithium salts were prepared in quantitative yield by ionic exchangebetween the potassium salt and lithium chloride in anhydroustetrahydrofurane.

These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers such as poly (ethyleneoxide). In this latter solvent, it has a conductivity higher than 2×10⁻⁴S·cm¹ at 60° C. for a concentration O/Li=12/1.

An electrochemical supercapacitance was prepared by utilizing a 1 Msolution of each of the above potassium salts in acetonitrile aselectrolytes and carbon/aluminum composites as electrodes. For eachsupercapacitance, the electrodes with a thickness of 150 μm were placedon both sides of a microporous polyethylene 40 μm thick impregnated witha potassium salt and the complete system was sealed in a glove box in abutton shaped battery housing. Good performances were obtained withthese supercapacitances (more than 100,000 cycles of charge/dischargebetween 0 and 2.5 V for a density of energy higher than 25 Wh/l and adelivered power higher than 1,500 W/I.

EXAMPLE 39 Alkylsulfonyl(trifluoromethanesulfonyl)imide

7.83 g (50 mmoles) of butanesulfonyl chloride C₄H₉SO₂Cl in solution in30 ml of anhydrous tetrahydrofurane at 0° C. were treated with 17.11 g(100 mmoles) of sodium trifluoromethanesulfonamide CF₃SO₂NHNa. After 1is hour at 0° C., and 24 hours at room temperature, the solvent wasevaporated and the product was reclaimed in 50 ml of water. An additionof 3.73 g of anhydrous potassium chloride KCl (50 mmoles) resulted inthe appearance of a precipitate which was recrystallized, and recoveredby filtration and finally dried. 9.37 g of potassiumtrifluoromethanesulfonyl(butanesulfonyl)imide (61% yield)C₄H₉SO₂NKSO₂CF₃ were thus obtained in the form of a crystallized whitepowder, having a purity determined by a fluorine and proton RMN higherthan 99%.

Microanalysis has given: H, 2.75 (2.95); C, 19.01 (19.54); N, 4.98(4.56); F, 18.21 (18.54); S, 20.25 (20.86); K, 12.56 (12.72).

Potassium trifluoromethanesulfonyl(octylsulfonyl)imide (I) and potassiumtrifluoromethanesulfonyl(dodecylsulfonyl)imide (II) were obtained underidentical conditions respectively from octylsulfonyl chloride anddodecylsulfonyl chloride.

The lithium salts of these three derivatives were prepared inquantitative yield by ionic exchange between the potassium salt andlithium chloride in anhydrous tetrahydrofurane. The lithium salt oftrifluoromethanesulfonyl(dodecylsulfonyl)imide dissolved in a matrix ofpoly (ethylene oxide) at a concentration O/Li=16/1 has a cationictransport number of about 0.55. The result is that when this compound isused as an electrolyte in a polymer electrolyte lithium battery, thegradients of concentration which appear during the operation of thebattery are decreased substantially. Performances during calls for powerare thus improved.

EXAMPLE 40 Octylsulfonyl(fluorosulfonyl)imide

5.16 g (25 mmoles) of octylsulfonyl chloride C₈H₁₇SO₂Cl in solution in20 ml of anhydrous tetrahydrofurane at 0° C. were treated with 6.86 g(50 mmoles) of potassium fluorosulfonamide. After 1 hour at 0° C. and 24hours at room temperature, the solvent was evaporated and the productwas recrystallized in 15 ml of water. After filtration and drying, 5.64g of potassium fluorosulfonyl(butanesulfonyl) imide C₈H₁₇SO₂NKSO₂F (72%yield) having a purity determined by a fluorine and proton RMN higherthan 99% was recovered. The lithium salt was prepared by ionic exchange(metathesis) between the potassium salt and lithium chloride inanhydrous tetrahydrofurane.

Microanalysis has given: H, 5.27 (5.47); C, 30.98 (30.66); N, 4.78(4.47); F, 6.52 (6.06); S, 20.96 (20.46); K, 12.01 (12.47).

The lanthanum salt of fluorosulfonyl(butanesulfonyl)imide C₈H₁₇SO₂NKSO₂Fmay be used as catalyst for Diels-Alder reactions, in particular indichloromethane.

These salts possess plasticizing properties.

EXAMPLE 41 Triisopropylsulfonyl(fluorosulfonyl)imide

3.96 g of fluorosulfonamide FSO₂NH₂ (40 mmoles) and 12.11 g of2,4,6-triisopropylbenzenesulfonyl chloride (40 mmoles, commerciallyavailable from Aldrich), were stirred in 40 ml of anhydroustetrahydrofurane at 0° C. in the presence of 8.49 g of anhydrouspotassium phosphate K₃PO₄. After 3 hours at 0° C., and 48 hours at roomtemperature, the solvent was evaporated and the product was reclaimed in24 ml of cold water. The addition of 2.98 g of anhydrous potassiumchloride gave a precipitate which was recrystallized, recovered byfiltration, and dried. There is thus obtained 11.78 g of potassiumfluorosulfonyl fluorosulfonyl (2,4,6-triisopropyl-benzenesulfonyl)imide(73% yield) having a purity determined by a fluorine and proton RMNhigher than 98%.

Microanalysis has given: H, 5.58 (5.98); C, 44.14 (44.53); N, 3.78(3.46); F, 5.02 (4.7); S, 15.23 (15.85); K, 10.21 (9.66).

The lithium salt was prepared by ionic exchange (metathesis) between thepotassium salt and lithium chloride in anhydrous tetrahydrofurane.

EXAMPLE 421-dodecyl-1,1,1,3,3,3-hexafluoro-2-propanoxysulfonyl(trifluoromethanesulfonyl)imide

By operating in a glove box under argon, 18.96 g (50 mmoles) oftrifluoromethanesulfonyl(1,1,1,3,3,3-hexafluoro-2-propanoxy-sulfonyl)imideprepared as in Example 37, were placed in solution in 20 ml of anhydroustetrahydrofurane. After having brought this solution to −20° C., 10 mlof a 1 M solution of potassium tert-butoxide (CH₃)₃COK (100 mmoles,commercially available from Aldrich) in tetrahydrofurane were addedslowly. After 15 minutes, 12.46 g of 1-bromododecane (50 mmoles) wereadded. The reaction is continued for 2 hours at −20° C., then during 24hours at room temperature. After 48 hours, the solvent was evaporatedand the residue was recrystallized in 50 ml of water containing 7.46 g(100 mmoles) of potassium chloride KCl. After filtration and drying,there is obtained potassium1-dodecyl-1,1,1,3,3,3-hexafluoro-2-propanoxysulfonyl-(trifluoromethanesulfonyl)imideof a purity characterized by a proton and fluorine RMN higher than 99%.

Microanalysis has given: H, 4.8 (4.5); C, 34.5 (34.1); N, 2.8 (2.3); F,28.1 (28.5); S, 10.1 (10.7); K, 6.1 (6.5).

The lithium salt was obtained in quantitative yield by treating thepotassium salt in anhydrous tetrahydrofurane by a stoichiometricquantity of anhydrous lithium chloride, filtration of the reactionmixture, evaporation of the solvent and drying under vacuum.

These salts may be used as additives for laminating lithium and for theextrusion of polymers, in particular the extrusion of poly (ethyleneoxide). They have plasticizing properties.

EXAMPLE 43 Igepal® CA-520-propylsulfonyl(trifluoromethanesulfonyl)imide

In 30 ml of tetrahydrofurane, 4.27 g of Igepal® CA-520 (10 mmoles,commercially available from Aldrich) were treated with 3.29 (10 mmoles)of trifluoromethanesulfonyl(3-chloropropanesulfonyl)-imide obtained asin Example 8, in the presence of 4.24 g of potassium phosphate K₃PO₄ (20mmoles). After 72 hours under stirring at 60° C., the reaction mixturewas filtered so as to remove potassium phosphate and potassium chlorideformed during the reaction. After evaporation of the solvent and drying,7.18 g of potassium Igepal®CA-520-propylsulfonyl(trifluoromethanesulfonyl)imide having a puritydetermined by proton and fluorine RMN higher than 96% were recovered.

Microanalysis has given: H, 6.89 (6.6); C, 46.45 (46.85); N, 1.69(1.95); F, 7.66 (7.94); S, 8.72 (8.93); K, 5.75 (5.45).

This salt is an excellent additive for the extrusion of poly (ethyleneoxide). It also enables to plasticize a large number of polymerscontaining polar units (ether, amide, nitrile, ester . . . ), whilegiving them a high ionic conductivity.

EXAMPLE 44 Toluenesulfonyl(trifluoromethanesulfonyl)imide

By operating in a glove box under argon, 3.23 g ofdichlorotriphenylphosphorane (C₆H₅)₃PCl₂ (10 mmoles) were added byportions to a solution of 2.24 g (20 mmoles) of DABCO and 1.49 g oftrifluoromethanesulfonamide CF₃SO₂NH₂ (10 mmoles) in 20 ml ofacetonitrile. After 3 hours under stirring, the reaction mixture wasfiltered to remove the precipitate of DABCO chloride formed, and thesolvent was evaporated. There was recovered a quantitative yield oftriphenylphosphoranylidene-sulfonyltrifluoromethyl CF₃SO₂N═P(C₆H₅)₃ inquantitative yield. Then, this compound was reacted with 1.94 g (10mmoles) of the sodium salt of p-toluenesulfonic acid in 10 ml ofdimethylformamide at 60° C. After 48 hours under stirring, the solventwas evaporated and the residue was recrystallized in 10 ml of watercontaining 1 g of potassium chloride KCl. After filtration and drying,2.46 g of sodium p-toluenesulfonyl(trifluoromethanesulfonyl)imide (76%yield) having a purity determined by a proton and fluorine RMN higherthan 99% were recovered.

Microanalysis has given: H, 2.07 (2.17); C, 29.88 (29.54); N, 4.01(4.31); F, 17.23 (17.52); Na, 7.15 (7.07); S, 19.21 (19.71).

EXAMPLE 45O,O′-[propylsulfonyl(trifluoromethanesulfonyl)imide]polyethylene Glycol

A sulfonated oligomer of poly(ethylene oxide) was prepared as follows:12 g of poly(ethylene glycol) of molecular weight 600 (=40 mmoles ofhydroxyl functions) were dried by azeotropic distillation with benzeneand by lyophilization. After addition of 50 ml of anhydroustetrahydrofurane, the terminal hydroxyl groups were metal substitutedwith potassium-naphthalene. The stoichiometry was determined bycolorimetry, and the end of the reaction was indicated by a persistenceof an intense green color of the anion radical of naphthalene. Then,4.89 g of 1,3-propane sultone (40 mmoles) were added. After evaporationof the solvent, the α,ω-disulfonated polymer was obtained in the form ofpowder and the residual naphthalene was removed by washing with hexane.8.44 g of the product thus formed (≈20 mmoles of —SO₃H), in suspensionin 20 ml of anhydrous acetonitrile, were treated with 2.82 g of(chloromethylene)dimethylammonium chloride [(CH₃)₂N═CHCl]⁺, Cl⁻ (22mmoles, commercially available from Aldrich). A precipitate of potassiumchloride was formed after about 1 h. 3.28 g oftrifluoromethanesulfonamiide (22 mmoles) and 2.47 g of DABCO (22 mmoles)were added to this suspension. After filtration, the reaction mixturewas stirred in the presence of 3.4 g of lithium phosphate Li₃PO₄ during24 hours. A new filtration followed by a reprecipitation in 200 ml etherat 0° C. has enabled to recover a viscous fluid which is very lightlycolored, characterized by a proton and fluorine RMN as in the case ofthe di-lithium salt of poly(ethylene glycol)α,ω-trifluoromethanesulfonyl-(propanesulfonyl)imide:

This salt is soluble in most polar organic solvents (acetonitrile,tetrahydrofurane, DMF, . . . ) and it may be used to plasticize a largenumber of polymers containing polar units (ether, amide, nitrile, ester. . . ), while giving them a high ionic conductivity.

EXAMPLE 46Trifluoromethanesulfonyl(R(−)-1-phenyl-2,2,2-trifluoroethanoxysulfonyl)imide

5.96 g (40 mmoles) of trifluoromethanesulfonamide and 9.9 ml of pyridinein 60 ml of anhydrous dichloromethane were cooled to −15° C. 0.4 g (40mmoles) of sulfuryl chloride diluted in 10 ml of anhydrousdichloromethane were then added drop-wise, followed by 7.05 g (40mmoles) of R(−)-1-phenyl-2,2,2-trifluoroethanol (commercially availablefrom Fluka). The mixture was stirred for 1 hour at −15° C., and for 4hours at room temperature (25° C.) The reaction mixture was filtered andthe solvent was removed with a rotary evaporator. The product which wasrecovered was reclaimed in 20 ml of ethanol. A precipitate is formedafter the addition of 3.93 g (40 mmoles) of potassium acetate. Afterrecrystallization, filtration and drying, there is obtained 12.25 g ofpotassiumtrifluoromethanesulfonyl(R(−)-1-phenyl-2,2,2-trifluoroethanoxysulfonyl)imide(72% yield) having a purity characterized by a fluorine and proton RMNhigher than 98%.

Microanalysis has given: H, 1.65 (1.42); C, 25.21 (25.41); N, 3.55(3.29), F, 26.21 (26.8); S, 15.65 (15.07); K, 9.56 (9.19).

In the same manner, potassiumtrifluoromethanesulfonyl-(S(+)-1-phenyl-2,2,2-trifluoroethanoxysulfonyl)imide(66% yield) was obtained from R(−)-1-phenyl-2,2,2,-trifluoroethanol.

Lithium salts were obtained by ionic exchange (metathesis) intetrahydrofurane with lithium chloride.

Lanthanum salts were obtained by treating potassium salts with astoichiometric quantity of lanthanum perchlorate La(ClO₄)₃, 6H₂O in amixture of acetonitrile and isopropyl orthoformate intended to removethe water of crystallization from the salt of lanthanum. Afterfiltration to remove the precipitate of potassium perchlorate KClO₄ andevaporation of the solvent, the lanthanum salts of the two enantiomersoftrifluoromethanesulfonyl-(1-phenyl-2,2,2-trifluoroethanoxysulfonyl)imidewere recovered in quantitative yield.

These salts are soluble in most polar organic solvents (acetonitrile,tetrahydrofurane, DMF, . . . ) and in aprotic solvating polymers.

EXAMPLE 47Trifluoromethanesulfonyl(N-methoxybutyl-N-2-butyl-3-methyl)aminosulfonyl)imide

The two enantiomers of the potassium salt oftrifluoromethanesulfonyl(N-methoxybutyl-N-2-butyl-3-methyl)aminosulfonyl)imidewere obtained by a process similar to the one described in Example 28,from N-methoxybutyl-N-2-butyl-2-methylamine (commercially available fromAir Products) with a purity higher than 99% and a yield of 62%.

By the same process, potassium salts of the two enantiomers offluorosulfonyl(N-methoxybutyl-N-2-butyl-3-methyl)-aminosulfonyl)imidewere also obtained.

The lithium salts are obtained by ionic exchange (metathesis) intetrahydrofurane with lithium chloride.

By a process similar to the one described in Example 46, lanthanum saltsof the two enantiomers oftrifluoromethanesulfonyl-(N-methoxybutyl-N-2-butyl-3-methyl)aminosulfonyl)-(N-methoxybutyl-N-2-butyl-3-methyl)aminosulfonyl)imideand the two enantiomers offluorosulfonyl-(N-methoxybutyl-N-2-butyl-3-methyl)amino-sulfonyl imidewere obtained.

These salts are soluble in most polar organic solvents (acetonitrile,tetrahydrofurane, DMF, . . . ) and in aprotic solvating polymers.

EXAMPLE 48 Camphorsulfonyl(trifluoromethanesulfonyl)imide

According to a process similar to the one described in Example 39, thepotassium salt of(1R)-(−)-10-camphorsulfonyl(trifluoromethanesulfonyl)imide was obtainedfrom (1R)-(−)-10-camphorsulfonyl (commercially available from Aldrich),and potassium (1S)-(+)-10-camphorsulfonyl(trifluoromethanesulfonyl)imidewas obtained from (1S)-(+)-10-camphorsulfonyl chloride (commerciallyavailable from Aldrich) with yields higher than 70%. The purity of thecompounds obtained, determined by proton and fluorine RMN, is higherthan 99%.

The potassium salt of(1r)-(−)-10-camphorsulfonyl(perfluorobutanesulfonyl)imide and(1S)-(+)-10-camphorsulfonyl(perfluorobutanesulfonyl)imide were obtainedfrom perfluorobutanesulfonamide C4F₉SO₂NH₂ obtained in Example 4.

Lithium salts were obtained by ionic exchange (metathesis) intetrahydrofurane with lithium chloride.

By a process similar to the one described in Example 46, lanthanum saltsof (1R)-(−)-10-camphorsulfonyl(perfluorobutane-sulfonyl)imide and of(1s)-(+)-10-camphorsulfonyl(perfluorobutanesulfonyl)imide were obtained:

These salts are soluble in most polar organic solvents (acetonitrile,tetrahydrofurane, DMF, . . . ) and in aprotic solvating polymers.

EXAMPLE 49N-(1S)-(+)-ketopinic-acetylmethylsulfonyl(trifluoromethanesulfonyl)imide

By operating in a glove box under argon, 2.8 g (10 mmoles) of thepotassium salt of trifluoromethanesulfonyl(N-methyl-sulfonyl) imideCF₃SO₂NKSO₂NH(CH₃) obtained in Example 10, in solution in 5 ml ofanhydrous tetrahydrofurane, there is slowly added 10 ml of a 1 Msolution in tetrahydrofurane of potassium tert-butoxide (CH₃)₃COK (10mmoles).

At the same time, to 1.82 g (10 mmoles) of (1S)-(+)-ketopinic acid(commercially available from Aldrich) in solution in 10 ml of anhydrousacetonitrile, there is added 80 mg of lithium hydride LiH (10 mmoles),and after a few minutes, 1.27 g of oxalyl chloride ClCOCOCl (10 mmoles).After centrifugation, the solution of THF was poured into this solution.The reaction was continued 24 hours at room temperature. The reactionmixture was then filtered to remove the precipitate of potassiumchloride, and the solvent was evaporated and the product recrystallizedin 6 ml of water. After filtration and drying, 2.76 g of potassiumtrifluoromethanesulfonyl(N-(1S)-(+)-ketopinic-acetyl-N-methylsulfonyl)imide(62% yield) were obtained with a purity characterized by a proton andfluorine RMN higher than 99%.

The scandium salt was obtained by treating the potassium salt with astoichiometric quantity of scandium tetrafluoroborate Sc(BF₄)₃ inacetonitrile. After filtration to remove the precipitate of potassiumtetrafluoroborate KBF₄ and evaporation of the solvent, after drying, thescandium salt oftrifluoromethanesulfonyl(N-(1S)-(+)-ketopinic-acetyl-N-methylsulfonyl)imidewas recovered in quantitative yield.

EXAMPLE 50Dialkylaminosulfonyl(trifluoromethanesulfonyl)imide-diphenyliodonium

1.58 g (5 mmoles) of diphenyliodonium chloride (C₆H₅)₂ICl and 1.89 g ofpotassium trifluoromethanesulfonyl(dibutyl-aminosulfonyl)imide(C₄H₉)₂NSO₂NKSO₂CF₃ (5 mmoles) were stirred together during 24 hours inwater. By extraction of the aqueous phase with dichloromethane, afterevaporation is of dichloromethane and drying, 3.01 g of thediphenyliodonium salt oftrifluoromethanesulfonyl(dibutylaminosulfonyl)imide (97% yield) wereobtained with a purity characterized by a proton and fluorine RMN higherthan 99%.

By the same process, the diphenyliodonium salt oftrifluoromethanesulfonyl(N,N-di-3-ethylhexyl-aminosulfonyl)imide wasprepared with a yield of 98% and with a purity characterized by a protonand fluorine RMN higher than 99%.

These salts enable to initiate under the action of actinic radiation(light, γ rays, electron beams) a cationic cross-linking reaction ofmonomers rich in electrons (vinyl ethers, alkyl vinyl ethers).

They are soluble in most usual organic solvents (tetrahydrofurane,acetonitrile, dimethylformamide, ethyl acetate, glymes, . . . ) and inaprotic solvating polymers such as poly (ethylene oxide). They are alsosoluble to an extent of 10% by weight in reactive solvents such astriethyleneglycol divinyl ether. The properties of photo-initiation ofthese salts were tested by irradiating with U.V. radiation at 254 run, apower of 1,900 mW/cm², a solution of triethyleneglycol divinyl ethercontaining same at 1% by weight. After a few seconds under irradiation,the reactive solvent has solidified, this reaction being veryexothermal.

EXAMPLE 51(4-butoxybenzene)-[trifluoromethanesulphonyl-(4-phenylsulfonyl)imide)]-iodonium

To a solution of 4.49 g (40 mmoles) of DABDO and 2.98 g oftrifluoromethanesulfonamide CF₃SO₂NH₂ (20 mmoles), in 10 ml of anhydroustetrahydrofurane at 0° C., there is added 6.05 g of4-iodobenzenesulfonyl chloride IC₆H₄SO₂Cl (20 mmoles, Aldrich) dilutedin 5 ml of anhydrous tetrahydrofurane. After 2 hours at 0° C., thereaction was continued during 24 hours at room temperature. The DABCOhydrochloride formed during the reaction was removed by filtration on afritted glass of porosity No. 4. After evaporation of acetonitrile fromthe filtered solution, the product was reclaimed in 15 ml of cold waterand there was slowly added 1.49 g of anhydrous potassium chloride (20mmoles) in solution in 5 ml of water. A precipitate appeared which wascollected by filtration on a fritted glass of porosity No. 4. Afterdrying, 7.89 g of potassiumtrifluoromethanesulfonyl(4-iodobenzenesulfonyl)imide (87% yield) havinga purity characterized by a proton and fluorine RMN higher than 99% wererecovered.

This compound was oxidized into CF₃SO₂NKSO₂C₆H₄I(O₂CCH₃)₂(iodosoacetate) with a mixture of acetic acid, acetic anhydride andhydrogen peroxide according to the method of Yamada & al (DieMakromolecular Chemie, (1972), 152, 153-162). 5.71 g of the compoundthus prepared (10 mmoles) were suspended in a mixture of 15 ml ofmethanesulfonic acid and 4.51 g of butoxybenzene (30 mmoles) kept at 0°C. during 4 hours. The reaction product was poured into 300 ml ether andthe precipitate was separated by filtration, washed with ether anddried. There is thus obtained 4.62 g (82% yield) of a zwitterion of(4-butoxybenzene)-[trifluoromethanesulfonyl-(4-phenylsulfonyl)imide]iodonium[CF₃SO₂N⁻SO₂C₆H₄I⁺C₆H₄OC₄H₉] having a purity characterized by a protonand fluorine RMN higher than 97%.

By a similar process, the compound(4-butoxybenzene)-[pentafluoroethanesulfonyl-4(4-phenylsulfonyl)imide]iodoniumwas obtained from pentafluoroethanesulfonamide and(4-butoxy-benzene)-[perfluorobutanesulfonyl(4-phenyl-sulfonyl)imide]iodoniumfrom perfluorobutanesulfonamide. These compounds have analogousproperties to those of the compounds of Example 50 and may be used forthe same application.

EXAMPLE 52 Tetrakis(acetonitrile)palladium(II)trifluoromethanesulfonyl(N,N-di-2-ethylhexylaminosulfonyl)imide

2.22 g (5 mmoles) of tetrakis(acetonitrile)palladiumtetra-fluoroborate(II) (CH₃CN)₄Pd(BF₄)₂ (commercially available fromAldrich), in 30 ml of tetrahydrofurane were treated with 4.91 g ofpotassiumtrifluoromethanesulfonyl(N,N-di-2-ethylhexylaminosulfonyl)imide (10mmoles) obtained in Example 28. After 24 hours under stirring, thereaction mixture was filtered to remove the precipitate of potassiumtetrafluoroborate KBF₄, and the solvent was evaporated.Trifluoromethanesulfonyl-(N,N-di-2-ethylhexylaminosulfonyl)imide oftetrakis-(acetonitrile)palladium(II) was obtained in quantitative yield.

This salt is useful as catalyst for the vinyl polymerization ofnorbornene. Thus, norbornene was polymerized at room temperature innitromethane in the presence of 300 ppm of this salt. After 2 hours, thereaction mixture was reprecipitated in methanol. Polynorbornene wasobtained with a number average molecular weight of 420,000 with a yieldof 82%.

EXAMPLE 535-dimethylamino-1-naphthalenesulfonyl(trifluoromethanesulfonyl)imide

In 20 ml of anhydrous acetonitrile, 5.39 g (20 mmoles) of5-dimethylamino-1-naphthalenesulfonyl chloride (commercially availablefrom Aldrich) was reacted with 2.98 g (20 mmoles) oftrifluoromethane-sulfonamide CF₃SO₂NH₂ 4.49 g (40 mmoles) of DABCO.After 24 hours under stirring at room temperature, the reaction mixturewas filtered to remove the DABCO hydrochloride formed, and acetonitrilewas evaporated. The product obtained was recrystallized in 20 ml ofwater containing 2.98 g (40 mmoles) of potassium chloride. Afterfiltration and drying, 5.63 g of potassiumtrifluoromethane-sulfonyl(5-dimethylamino-1-naphthalenesulfonyl)imide(69% yield) was recovered with a purity characterized by a fluorine andproton RMN higher than 99%.

Microanalysis has given: H, 2.96 (2.88); C, 37.23 (37.14); N, 6.41(6.66); F, 13.98 (13.56); S, 15.65 (15.25); K, 9.46 (9.3).

This fluorescent salt is soluble in most polar organic solvents(acetonitrile, tetrahydrofurane, DMF, . . . ).

EXAMPLE 54 N-trifluoromethanesulfonyl-2-aminoacridine

Using a process similar to the one described in Example 34, themagnesium salt of N-trifluoromethanesulfonyl-2-aminoacridine wasobtained by action of trifluoromethanesulfonyl chloride on magnesium2-aminoacridine in tetrahydrofurane. After evaporation of the solvents,the product was reclaimed in water and treated with tetraethylammonium(10% in excess) in water, and a precipitate then appeared. Afterfiltration and drying, N-trifluoromethanesulfonyl-2-aminoacridinetetraethylammonium (66% yield) was obtained with a purity determined bya proton and fluorine RMN higher than 99%.

Microanalysis has given: H, 6.11 (6.39); C, 59.25 (59.85); N, 6.89(6.34); F, 12.25 (12.91); S, 7.95 (7.26).

In the same manner, N-fluorosulfonyl-2-aminoacridine tetraethylammoniumwas obtained from fluorosulfonamide.

This salt is soluble in most usual organic solvents (tetrahydrofurane,acetonitrile, dimethylformamide, ethyl acetate, glymes, . . . ) and inaprotic solvating polymers such as poly (ethylene oxide), as well as inpolymers with low polarity such as methyl polymethacrylate.

These salts have a very substantial fluorescence. A dichloroethanesolution of polymethyhmethacrylate (PMM) and of either of these ammoniumsalts (97:3) was prepared. Fluorescent deposits were obtained on anumber of supports (glass, polymer, . . . ).

EXAMPLE 55 1,3-phenylsulfonamide-N,N′-perfluoro-1-butanesulfonylrhodamine B

To 2.9 g of sulforhodamine B (5 mmoles, commercially available fromAldrich) in 50 ml of anhydrous dimethylformamide, there is added 941 mgof the potassium salt of trifluoromethanesulfonic acid CF₃SO₃K (5mmoles). After 2 hours under stirring, 1.27 g of oxalyl chlorideClCOCOCl (10 mmoles) in solution in 10 ml of anhydrous dichloromethanewas added slowly. The reaction was continued overnight under argon, and6.74 g of potassium perfluoro-1-butanesulfonamide C₄F₉SO₂NHK (20 mmoles)were added. After 48 hours, dimethylformamide was evaporated and theresidue was recrystallized in 40 ml of water. After filtration anddrying, there is obtained 4.11 g (71% yield) of the potassium salt of1,3-phenyl-sulfonamide-N,N′-(perfluoro-2-butanesulfonyl) rhodamine Bhaving a purity characterized by a proton and fluorine RMN higher than99%.

Microanalysis has given: H, 2.76 (2.52); C, 36.56 (36.27); N, 4.96(4.83); F, 29.99 (29.51); S, 11.55 (11.07); K, 3.17 (3.37).

By the same process, the di-potassium salt of1,3-phenylsulfonamide-N,N′-fluorosulfonyl rhodamine B was obtained fromthe potassium salt of fluorosulfonamide, the di-potassium salt of1,3-phenylsulfonamide-N,N′-trifluoromethanesulfonyl rhodamine B wasobtained from the potassium salt of trifluoromethanesulfonamide and thedi-potassium salt of1,3-phenylsulfonamide-N,N′-pentafluoroethane-sulfonyl rhodamine B wasobtained from pentafluorosulfonamide.

Lithium salts were obtained by metathesis with lithium chloride intetrahydrofurane.

These zwitterions have intense dying properties. They are soluble inpolar polymers and permit the production of colorants containing lasers.The sulfonimide groups also enable them to be adsorbed on oxides, inparticular nano-particular titanium dioxide; they then act as asensitizer towards visible radiation, in particular in applications tophotovoltaic cells.

EXAMPLE 56 Trifluoromethanesulfonyl(anthracenyl-9-ethanesulfonyl)imide

In a Parr chemical reactor, there is introduced a solution of 9.36 g ofthe potassium salt of trifluoromethanesulfonamide CF₃SO₂NHK (50 mmoles)and of 264 of crown ether, 18-Crown-6 (acting as complexing agent of thepotassium cation), in 60 ml of anhydrous acetonitrile. After closing thereactor, the reactor was flushed with argon during 15 minutes beforeisolating it. There is then introduced 6.41 g of sulfur dioxide SO₂ (50mmoles, commercially available from Fluka) and, after 10 minutes, 10.21g of 9-vinylanthracene (50 mmoles, commercially available fromLancaster) in solution in 20 ml of anhydrous dichloromethane. After 6hours at room temperature, the temperature of the reactor was set at 50°C. and kept therein during 48 hours, and the solvent was evaporated andthe product was dried. The potassium salt oftrifluoromethanesulfonyl(anthracenyl-9-ethanesulfonyl)imide wasrecovered in quantitative yields with a purity characterized by afluorine and proton RMN higher than 99%.

Microanalysis has given: H, 2.78(2.88); C, 44.53 (44.83); N, 3.33(3.07); F, 12.01 (12.51); S, 14.36 (14.08); K, 8.99 (8.58).

Using the same process, the potassium salt offlurosulfonyl(anthracenyl-9-ethanesulfonyl)imide was obtained.

This salt is soluble in most usual organic solvents (tetrahydrofurane,acetonitrile, dimethylformamide, ethyl acetate, glymes, . . . ) and inpolar polymers.

EXAMPLE 57N,N′,N″,N′″-perfluorobutanesulfonyl-nickel(II)phtalocyaninetetrasulfonamide

To 4.9 g of the sodium salt of Nickel(II)phthalocyaninetetrasulfonicacid (5 mmoles, commercially available from Aldrich) in 40 ml ofanhydrous dimethylformamide, there is slowly added 2.54 g of oxalylchloride ClCOCOCl (20 mmoles) in solution in 10 ml of anhydrousdichloromethane. After 4 hours under stirring, the reaction mixture wascentrifuged, the liquid floating on the surface was removed, and thedecanted product was reclaimed in 40 ml of anhydrous dimethylformamide.Then, 13.5 g of the potassium salt of perfluoro-1-butanesulfonamideC₄F₉SO₂NHK (40 mmoles) were added. After 48 hours, the dimethylformamidewas evaporated and the residue was recrystallized in 50 ml of watercontaining 1.49 g (20 mmoles) of anhydrous potassium chloride. Afterfiltration and drying, there is obtained 9.54 g (81% yield) of thepotassium salt of N,N′,N″,N′″-perfluorobutanesulfonyl-Nickel(II)phtalocyaninetetrasulfonamide having a purity characterized by a protonand fluorine RMN higher than 99%.

This salt is soluble in most usual organic solvents (tetrahydrofurane,acetonitrile, dimethylformamide, ethyl acetate, glymes, . . . ) and inpolar polymers to which it gives an intense blue color and which isstable towards light. This salt, as well as analogous nickel, iron ormanganese salts are useful as catalysts for the reduction of oxygen.

EXAMPLE 58

In 30 ml of THF, 6.76 g of pentafluoropyridine (40 mmoles, commerciallyavailable from Aldrich) are reacted with 7.49 g (40 mmoles) of thepotassium salt trifluoromethanesulfonamide CF₃SO₂NHK in the presence of4.49 g (40 mmoles) of DABCO. After 48 hours under stirring, the solventwas evaporated and the residue was recrystallized in 20 ml of water.After filtration and drying, 8.03 g of the potassium salt oftrifluoromethanesulfonyl(4-azapentafluoropyridine)amide (76% yield) wereobtained, having a purity determined by a fluorine RMN higher than 99%.

According to the same process, the potassium salt oftrifluoromethanesulfonyl((4,6-dinitro-2-trifluoromethyl)phenyl)amide wasobtained is from 10.82 g of 2-chloro-3,5-dinitrobenzo-trifluoride (40mmoles, commercially available from Aldrich), having a purity determinedby a fluorine, proton and carbon RMN higher than 99%.

Lithium salts were obtained by ionic exchange with lithium chloride inTHF.

These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in aprotic solvating polymers.

EXAMPLE 59N,N′-trifluoromethanesulfonyl-3,4-amino-3-cyclobutene-1,2-dione

In a glove box under argon, 5.61 g (30 mmoles) oftrifluoromethanesulfonamide in solution in 40 ml of anhydroustetrahydrofurane at −30° C., there is added drop-wise 30 ml of a 1 Msolution of dibutylmagnesium (C₄H₉)₂Mg (30 mmoles, commerciallyavailable from Aldrich) in heptane. After 4 hours at −30° C., there isslowly added 2.55 g (15 mmoles) of 3,4-diethoxy-3-cyclobutene-1,2-dione.The reaction was continued during 2 hours at −30° C. and for 24 hours atroom temperature. The solvents were then evaporated, the product wasreclaimed in water and extracted with ether after acidification of theaqueous solution. The compound obtained after evaporation of ether wassublimated under secondary vacuum at 40° C., and after 24 hours 5.02 gof N,N′-trifluoromethanesulfonyl-3,4-amino-3-cyclobutene-1,2-dione (89%yield) were recovered on a cold finger.

Microanalysis has given: H, 0.78 (0.54); C, 18.89 (19.16); N, 7.04(7.45); F, 29.88 (30.3); S, 16.71 (17.04).

The lithium salt was obtained by treating the acid with lithiumcarbonate Li₂CO₃ in water.

These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in polar polymers.

These salts have two reversible redox couples, they are reoxidized to isneutral state at the potential of oxidation of LiCoO₂ at the end of thecharge. By dissolution in a liquid, gel or polymer electrolyte, theyprovide for a protection during overcharge, thus acting as a redoxshuttle. They also make it possible to produce electrochrome systemswith colorants.

EXAMPLE 60 1,1′-(propylsulfonamide-N-trifluoromethanesulfonyl)ferrocene

During a first step, a ferrocene dilithium complexed withtetramethylethylenediamine (TMEDA) was prepared in the following manner:by operating in a glove box under argon, 37 ml of TMEDA (247 mmoles)freshly distilled and 40 ml of anhydrous hexane were placed in a 1 litreflask. Then, 154 ml of a 1.6 M solution of butyllithium in hexane (247mmoles, commercially available from Aldrich) were added drop-wise. After10 minutes, 18.6 g of ferrocene (100 mmoles) in solution in 500 ml ofanhydrous hexane were added drop-wise while maintaining a strongstirring of the solution. After standing overnight, orange crystalsappeared in the solution, which were recovered by filtration of thesolution on a fritted glass of porosity No. 4. After drying undervacuum, there is obtained 28.4 g of 1,1′-dilithio-ferrocene.2 TMEDA (66%yield) which are kept under argon.

8.61 g of this compound (20 mmoles) in 30 ml of anhydrous acetonitrilewere thereafter treated with 4.89 g of 1,3-propane sultone (40 mmoles)in a glove box. After 24 hours at room temperature, 2 drops ofdimethylformamide were added into the reaction mixture, and 5.08 g ofoxalyl chloride ClCOCOCl (40 mmoles) in solution in 15 ml of anhydrousdichloromethane were added slowly. After 4 hours at room temperature,14.97 g of the potassium salt of trifluoromethanesulfonamide (80 mmoles)were added. The reaction continued for 24 hours, then the solvent wasevaporated. The compound collected was then recrystallized in 30 ml ofwater containing 3 g of potassium chloride. After filtration and drying,10.2 g of a di-potassium salt of1,1′-(propylsulfonamide-N-trifluoromethane-sulfonyl)ferrocene (66%yield) were recovered, in which the purity is characterized by a protonand fluorine RMN higher than 97%.

Microanalysis has given: H, 2.38 (2.62); C, 28.72 (28.13); N, 3.13(3.64); F, 15.16 (14.83); S, 17.12 (16.68); K, 10.56 (10.17); Fe, 7.65(7.27).

By a similar process, the di-potassium salt of1,1′-(propylsulfonamide-N-fluorosulfonyl)ferrocene was obtained.

Lithium salts were obtained by treating the acid with lithium carbonateLi₂CO₃ in water.

These salts are soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in polar polymers.

These salts have a reversible redox couple. In poly (ethylene oxide) areversible potential ≈3.4 V towards a lithium electrode was determinedon a platinum electrode having a diameter of 125 μm.

By dissolution into a liquid, gel or polymer electrolyte, the salts gaveprotection during overcharge, thus acting as a redox shuttle. They alsoenable to produce electrochrome systems with colorants.

EXAMPLE 61 9-10-(propylsulfonamide-N-trifluoromethane-sulfonyl)phenazine

By operating in a glove box under argon, there is introduced into aNalgene 30 ml flask 1.8 g of phenazine (10 mmoles) and 139 mg ofmetallic lithium. Then, there is added 20 ml of anhydroustetrahydrofurane and agate balls. After closing the flask, it wasrotated upon itself, outside the glove box, on the shaft of a motor.Tetrahydrofurane rapidly turned to a dark purple color, whichcharacterizes mono-lithium phenazine. After 24 hours, there is obtainedin suspension an orange precipitate of 9,10-di-Li-dihydrophenazine. 6.56g of the potassium salt oftrifluoromethanesulfonyl(3-chloropropanesulfonyl)imide (20 mmoles),obtained in Example 8, were then added under argon. The flask was thenagain rotated upon itself during 24 hours, and the reaction mixture wasfiltered under argon to remove the precipitate of potassium chloridewhich is formed during the reaction, and the balls of agate.

After evaporation of the solvent, 6.52 g of the di-lithium salt of9-10-(propylsulfonamide-N-trifluoromethanesulfonyl)phenazine wererecovered.

This salt is soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes, . . . ) and in polar polymers.

This salt has two reversible redox couples. In poly (ethylene oxide), ona platinum electrode of a diameter of 125 μm, it was shown that there isa first redox couple having a potential ≈3.2 V and a second redox couplehaving a potential ≈3.8 V, these potentials being measured towards alithium electrode.

By dissolution in a liquid, gel or polymer electrolyte, this saltprovides protection in overcharge, thus acting as a redox shuttle.

This salt may also be used in electrochrome systems with colorants. Itwas thus possible to produce an electrochrome glass pane by depositingon a glass plate covered with a conductive layer of ITO (indium and tinoxide), a solution in acetone of this compound andpoly(benzodiimide-co-oxide of ethylene) having a molecular weight ≈1,100g/mole. After evaporation of the solvent and drying, in a glove box,there is deposited on the layer of copolymer, a second glass electrodecovered with a conductive layer of ITO (indium and tin oxide). Afterhaving sealed the assembly to make it impervious, a potential of 1.250mV was applied on the outside by means of a potentiostat. The system wasthen colored in intense blue. By applying a potential of −500 mV, arelatively rapid discoloration of the system (lower than 60 s) wasnoted.

Such an electrochrome system is easy to prepare, even for large sizesystems (larger than m²) which use either a glass or a polymer which issuitably treated as a conductive transparent electrode. Moreover, theenergy required to maintain the coloration is relatively low, i.e. lowerthan 1 W/m².

EXAMPLE 62 2,2′-Azinobis(3-ethylbenzothiazoline-6(sulfonyl(trifluoromethanesulfonyl)imide)

First, the di-sodium salt of2,2′-azinobis(3-ethylbenzo-thiazoline-6-sulfonic) acid was prepared fromits di-ammonium salt (commercially available from Aldrich), by treatingit with a titrated solution of sodium hydroxide. After evaporation anddrying, the di-sodium salt was recovered in quantitative yield. To 1.12g of this compound (2 mmoles) in 10 ml of anhydrous acetonitrile, thereis slowly added 508 mg of oxalyl chloride ClCOCOCl (4 mmoles) insolution in 1 ml of anhydrous dichloromethane. After 4 hours understirring, there is added 2.7 g of the potassium salt ofperfluoro-1-butanesulfonamide C₄F₉SO₂NHK (4 mmoles). After 48 hours, theacetonitrile was evaporated and the residue was recrystallized in 10 mlof water. After filtration and drying, there is obtained 1.81 g of thefollowing compound:

The di-tetraethylammonium salt was prepared by treating this productwith tetraethylammonium chloride in water. The di-tetraethylammoniumsalt was thereafter recovered by extraction with dichloromethane.

By oxidation, this compound gives a radical and a biradical which arestable zwitterions. In addition, this compound is useful as oxidationcatalyst between an oxygenated aqueous phase and a non-miscible organicphase containing the species to be oxidized.

EXAMPLE 63 Poly(N-2-trifluoromethanesulfonyl-aniline)

To 21.63 g of 1,2-phenylenediamine C₆H₄(NH₂)₂ (200 mmoles), in 200 ml ofanhydrous dichloromethane at −20° C., there is added drop-wise 56.42 gof trifluoromethanesulfonic anhydride (CF₃SO₂)₂O (200 mmoles) insolution in 50 ml of anhydrous dichloromethane. After standing overnightat −20° C. and 4 hours at room temperature, the dichloromethane wasevaporated. The residue was then recrystallized in 10 ml of a 4 Msolution of potassium hydroxide KOH. After filtration and drying, 47.87g of the potassium salt ofN-2-trifluoromethanesulfonyl-1,2-phenylenediamine was recovered (86%yield). This compound (172 mmoles) was then stirred in 86 ml of a 2 Msolution of hydrochloric acid. After 24 hours, and after filtration anddrying, 26.85 g (65% yield) of the ammonium salt ofN-2-trifluoromethanesulfonyl-1,2-phenylenediamine C₆H₄(NSO₂CF₃)(NH₃+)were recovered. 12.01 g of this compound (50 mmoles) were then dissolvedin 200 ml of water, 136 mg of silver nitrate (800 mmoles) were added,and the solution was brought to 0° C. A solution of 11.4 g of ammoniumpersulfate (NH₄)₂S₂O₈ (50 mmoles) in 100 ml of water was also preparedand this solution was brought to a temperature of 0° C. Then thepersulfate solution was added under stirring for a few minutes to asolution of the aniline salt. After about 10 minutes, the solutionstarted to assume a color. After 3 hours at a temperature lower than 5°C., the solution was concentrated to a volume 100 ml and 3.73 g ofpotassium chloride were added. The precipitate present in the solutionwas then recovered by filtration. After drying, 5.9 g of the followingblack powder was obtained:

This electronically conductive polymer has an electronic conductivitydetermined by the method of four peaks of 8.7 S·cm¹. This conductivityis stable even when the material is exposed to air.

EXAMPLE 641-dodecyl-1,1,1,3,3,3-hexafluoro-2-propanoxysulfonyl(trifluoromethanesulfonyl)imide

To 18.11 g (100 mmoles) of 6-bromo-1-hexanol and 11.22 g (100 mmoles) ofDABCO in 100 ml of anhydrous THF at −20° C. there is slowly added 19.06g (100 mmoles) of tosyl chloride. After 24 hours under stirring at −20°C., the reaction mixture was filtered to remove the precipitate of DABCOhydrochloride. After evaporation of the solvent, 6-bromo-1-hexanoltosylate CH₃ΦSO₂O(CH₂)₆Br was recovered quantitatively. This compoundwas thereafter dissolved in 200 ml of THF with 40 g of aniline ΦNH₂ andthis solution was brought to reflux overnight. After cooling, 300 ml ofwater were added and the organic phase was extracted with ether. Afterwashing with water, the ether phase was dried with magnesium sulfate.There is obtained, after evaporation and drying, 23 g ofN-(6-bromohexyl)aniline.

By operating in a glove box under argon, 18.96 g (50 mmoles) oftrifluoromethanesulfonyl(1,1,1,3,3,3-hexafluoro-2-propanoxysulfonyl)imide,prepared as in Example 37, were put in solution in 10 ml of anhydroustetrahydrofurane. After having brought this solution to −20° C., 50 mlof a 1 M solution in tetrahydrofurane of potassium tert-butoxide(CH₃)₃COK (50 mmoles, commercially available from Aldrich) were slowlyadded. After 15 minutes, 12.81 g (50 mmoles) of N-(6-bromohexyl)anilinewere added. The reaction was continued during 2 hours at −20° C., thenfor 24 hours at room temperature. After 48 hours under stirring, thesolvent was evaporated and the residue was recrystallized in 30 ml ofwater. After filtration and drying, the potassium salt of1-(6-anilino-1-hexyl)-1,1,1,3,3,3-hexafluoro-2-propanoxysulfonyl(trifluoromethanesulfonyl)imidewas obtained, which has a purity characterized by a proton, carbon andfluorine RMN higher than 97%.

12.13 g of this compound (20 mmoles) were thereafter dissolved in 20 mlof water, 68 mg of silver nitrate (400 μmoles) were added, and thetemperature of the solution was brought to 0° C. Also, a solution of4.56 g of ammonium persulfate (NH₄)₂S₂O₈ (20 mmoles) in 100 ml of waterwas prepared and this solution was brought to 0° C. Then, the solutionof persulfate was added during a few minutes to the solution of the saltof aniline under stirring. After about 10 minutes, the solution startedto turn to a bluish green color. After 3 hours at a temperature lowerthan 5° C., the solution was concentrated to a volume ≈60 ml, and 1.49 gof potassium chloride were added. The precipitate present in thesolution was then recovered by filtration. After drying, there isobtained 3.9 g of a black powder of the following compound:

This polymeric compound which comprises a doping anion very delocalizedin its structure, has the properties of an electronic conductor (PCE).The low basic character of this anion improves the stability of thepolymer, in particular in humid medium. The conductivity determined by afour peaks measurement, before exposing the PCE to a humid atmosphere,was of the order of 4 S·cm⁻¹.

This material was tested as a cathode for a battery. The battery had thefollowing structure:

-   -   a composite cathode consisting of 40% by volume of the copolymer        obtained in the present example and 60% by volume of poly        (ethylene oxide) of molecular weight 3×10⁵;    -   an electrolyte consisting of a poly (ethylene oxide) film of        molecular weight 5×10⁶ the lithium salt of        trifluoromethanesulfonyl-(butanesulfonyl)imide, obtained in        Example 39, at a concentration O/Li=20/1;    -   a metallic lithium anode.

After mounting the assembly in a button shaped battery casing, thebattery obtained was cycled at a temperature of 60° C. between 3 V and3.9 V. More than 1,000 cycles of charge/discharge were carried out whilepreserving 80% of the capacity of the first cycle.

In addition, the polymeric compound of the present example is a goodcorrosion inhibitor of ferrous metals in acid or chloride media. Thetreatment of surfaces to be protected is simply carried out bydepositing a solution of PCE in a mixture of water anddimethylformamide, in the form of a paint, followed by drying andthermal treatment at 100° C. This polymeric compound gives adherentconductive deposits whose conductivity is stable in air on plasticstreated by Corona effect.

EXAMPLE 65Poly(2-[2-(3-thienyl)ethoxy]ethanesulfonyl(trifluoromethanesulfonyl)imide)

By a process similar to the one used for the synthesis of7,8-octene-3,6-oxa-1-sulfonyl-(trifluoromethanesulfonyl)imide (Example15), the potassium salt of2-[2-3(3-thienyl)ethoxy]-ethane-sulfonyl(trifluoromethanesulfonyl)imidewas synthesized from 2-(3-thienyl)ethanol. The product obtained has apurity determined by a carbon and proton RMN higher than 98%.

10 ml of a 5×10⁻² M solution of the salt in acetonitrile was preparedand electropolymerization was carried out in the anode compartment of anelectrochemical cell on an electrode of platinum. There is obtained aconductive flexible film of:

in which the doping (oxidation) is ensured by cation and electronexchange with the exterior. The conductivity of this material is of theorder of 10 S·cm⁻¹ and it is stable at ambient atmosphere and in humidmedium. An electropolymerization carried out in the presence ofnon-substituted pyrrol or having oxyethylene chains in N or 3 positiongives copolymers which are also stable in which the change of color maybe used for preparing electrochrome system.

EXAMPLE 66 Doped Polyaniline

In 100 ml of water there is suspended 2.54 g of polyaniline chloride(AC&T, St Égrève, France):

To 9.81 g of the potassium salt oftrifluoromethanesulfonyl(di-2-ethylhexylaminosulfonyl)imide obtained inExample 28 were then added:

After 48 hours under stirring, the polyaniline doped withtrifluoromethanesulfonyl)di-2-ethylhexylaminosulfonyl)imide wasrecovered. In this form, it is soluble in toluene. A toluene solution ofthe doped polyaniline was used to produce a film which is anelectronically conductive polymer in which the conductivity, measured bythe method the four peaks, is 6 S/cm, with a good stability in humidmedium.

From this solution, there is also prepared a film on a support ofpolypropylene (PP) treated by Corona effect. After drying under vacuumat 60° C. during 48 hours, there is obtained a deposit of polyanilinewhich is conductive and adherent and has a thickness lower than 1micron. This type of treatment on plastic materials is particularlyinteresting to produce flexible electrical contactors or systems ofelectromagnetic protections.

EXAMPLE 67 Poly(4-styrenesulfonyl(trifluroro methane sulfonyl)imide)

20.62 g of poly(sodium-4-styrenesulfonate) having an average molecularweight of 10⁶ g/mole (100 mmoles of —SO₃Na), (commercially availablefrom Aldrich) in suspension in 100 ml of anhydrous dimethylformamidewere treated with 14.08 g (110 mmoles) of(chloromethylene)dimethylammonium chloride (commercially available fromAldrich) at room temperature. After 72 hours, the solution becameviscous, and the poly(4-styrenesulfonyl chloride) goes into solution indimethylformamide. To the reaction mixture there is then added 16.4 g(110 mmoles) of trifluoromethanesulfonamide and 24.68 g (220 mmoles) of1 (DABCO). After 24 hours, the solvent was evaporated, the productobtained was reclaimed in 50 ml of water, and treated with 8.2 g ofanhydrous potassium chloride. After 24 hours, the reaction mixture wasfiltered and the product thus recovered was recrystallized in 50 ml ofwater. After drying, there is obtained 26.1 g of the potassium salt ofpoly(4-styrenesulfonyl(trifluoromethanesulfonyl)-imide) (74% yield)having a purity characterized by a proton and fluorine RMN higher than99%.

The corresponding lithium salt was prepared quantitatively by ionicexchange (metathesis) between the potassium salt and lithium chloride inanhydrous tetrahydrofurane.

This polyelectrolyte is soluble in most of the usual organic solvents(tetrahydrofurane, acetonitrile, dimethylformamide, ethyl acetate,glymes) and in polar polymers.

By utilizing an appropriate cation, this polyelectrolyte may constitutea doping agent of conjugated electronically conductive polymers such aspolypyrrol or polyaniline.

EXAMPLE 68 Catalysis of an Aldol Condensation

Diethylaminosulfonyl(trifluoromethanesulfonyl)imide was prepared fromits potassium salt, obtained in Example 28, according to a processsimilar to the one used in Example 29 to givedimethylaminosulfonyl(trifluoromethanesulfonyl)imide. Following this,2.84 g of this acid (10 mmoles) were treated with 657 mg of ytterbiumoxide Yb₂O₃ (1.67 mmoles) in 20 ml of water. After 24 hours of stirring,the solution was lyophilized, and the product obtained was dried undervacuum during 48 hours at 60° C. The ytterbium salt ofdiethylaminosulfonyl(trifluoromethanesulfonyl)imide (Yb(DETFSI)₃) wasobtained in quantitative yield.

This salt was used as a catalyst for an aldol condensation in thefollowing manner:

To 410 mg of Yb(DETFSI)₃ (0.4 mmoles, 10% molar) in dichloromethanethere is added a mixture of 1.05 g (6 mmoles) of1-ene-3-methyl-1-silylacetal-1-methoxypropene (CH₃)₂C═C(OSiMe₃)OMe and420 mg (4 mmoles) of benzaldehyde in 10 ml of dichloromethane. After 16hours under string at room temperature, water was added and the productwas extracted with dichloromethane. The organic phase was washed withthree fractions of 100 ml of water, and dichloromethane was evaporated.The residue was then treated with a mixture tetrahydrofurane/HCl 1 M(20:1) during 0.5 hours at 0° C. After diluting with hexane, a saturatedsolution of sodium bicarbonate was added, and the product was extractedwith dichloromethane. The organic phase was washed with a saturatedsolution of sodium chloride, and dried with sodium sulfate. Afterevaporation of the solvents, the raw product was chromatographed on asilica gel. Methyl-3-hydroxy-2,2-dimethyl-phenylpropionate was obtainedwith a yield of 89%.

The same reaction was carried out with a quantity of catalysts which isdecreased by a factor near 10, without decreasing the yield of thecompound methyl-3-hydroxy-2,2-dimethyl-phenylpropionate. This result isdue to the good solubility in dichloromethane of the ytterbium salt ofdiethylaminosulfonyl(trifluoromethanesulfonyl)imide.

EXAMPLE 69 Catalysis of a Michael Addition

The ytterbium salt ofdiethylaminosulfonyl(trifluoromethanesulfonyl)imide, obtained in Example40, was used as a catalyst in a Michael addition in the followingmanner: To 410 mg of Yb(DETFSI)₃ (0.4 mmoles, 10% molar), obtained inExample 65 in 15 ml of dichloromethane, there is added a mixture of 1.05g of 1-ene-2-methyl-1-silylacetal-1-methoxypropane (CH₃)₂C═C(OSiMe₃)OMe(6 mmoles) and 840 mg of chalcone (4 mmoles) in 10 ml ofdichloromethane. After 12 hours under stirring at room temperature,water is added and the product was extracted with dichloromethane. Theorganic phase was washed with three fractions of 100 ml of water, anddichloromethane was evaporated. The residue was then treated with amixture of tetrahydrofurane/HCl 1 M (20:1) during 0.5 hours at 0° C.After diluting with hexane, there is added a saturated solution ofsodium bicarbonate, the product was extracted with dichloromethane. Theorganic phase was washed with a saturated solution of sodium chloride,and dried with sodium sulfate. After evaporation of the solvents, theraw product was chromatographed on a silica gel. The compound1,5-dicarbonyl was obtained with a yield of 87%.

The same reaction was carried out with a quantity of catalyst which isdecreased by a factor close to 10, without decreasing the yield of the1,5-dicarbonyl compound. This result is due to the good solubility indichloromethane of the ytterbium salt ofdiethylaminosulfonyl(trifluoromethanesulfonyl)imide.

EXAMPLE 70 Catalysis of a Friedel-Crafts Acylation Reaction

To 10 ml of a 1 M solution of triethylaluminum (C₂H₅)₃Al (10 mmoles)(commercially available from Aldrich in toluene, there is slowly addedunder argon 2.84 g oftrifluoromethanesulfonyl(diethylaminosulfonyl)imide (C₂H₅)₂NSO₂NHSO₂CF₃(10 mmoles) in solution in 10 ml of toluene, hereinafter designatedHDETFSI, previously prepared from the corresponding potassium salt byextraction with ether. After 2 hours under stirring, the solvent wasevaporated and the corresponding aluminum salt was dried and stored in aglove box.

This compound was used as catalyst for a Friedel-Crafts acylationreaction in the following manner; in 40 ml of anhydrous nitromethane,there is added 616 mg of Al(DETFSI)₃ (700 μmoles), and 1.08 g of anisol(10 mmoles) and 2.04 g of acetic anhydride. After stirring for 5 minutesat 21° C., the reaction mixture was diluted with 50 ml of ether and thereaction was inhibited with 100 ml of a saturated solution of sodiumbicarbonate NaHCO₃. After filtration on Celite, the solution wasextracted with three fractions of 50 ml of ether, and the ether phasewhich was collected was washed with a saturated solution of potassiumchloride. After drying the ether phase with magnesium sulfate andevaporation, 1.46 g of p-methoxyacetophenone (97% yield) were recoveredwith a purity characterized by a proton RMN higher than 99%.

EXAMPLE 71 Catalysis of a Diels & Alder Reaction

Various salts according to the invention were used as catalysts of aDiels Alder reaction, namely the reaction of methylvinylketone withcyclopentadiene.

The salts used are the lanthanum salt oftrifiuoromethanesulfonyl(R(−)-1-phenyl-2,2,-trifluoroethanoxysulfonyl)imide(LaPTETFSI) prepared according to Example 46, the lanthanum salt of(1R)-(−)-10-camphorsulfonyl)perfluorobutanesulfonyl)imide (LaCSTFSI)prepared according to Example 48, the lanthanum salt of(1R)-(−)-trifluoromethanesulfonyl(N-methoxybutyl-N-2-butyl-3-methyl)aminosulfonyl)imide(LaMBBMTFSI) prepared according to Example 47 and the scandium salt oftrifluoromethanesulfonyl(N-(1S)-(+)-ketopinic-acetyl-N-methylsulfonyl)imide (ScKANTFSI) preparedaccording to Example 49.

For each of the above salt, the following process was used.

To a solution of 651 mg of freshly distilled cyclopentadiene (10 mmoles)and 701 mg of methylvinylketone in 10 ml of dichloromethane, there areadded 200 μmoles of the lanthanum or scandium salt of chiral. After 24hours at room temperature, the reaction mixture was filtered to removethe catalyst in suspension. In all cases, there is obtained a yield,determined by chromatography in gaseous phase, higher than 90%. Afterseparating the different reaction products on a chiral column, theenantiomeric excesses were determined by RMN. These salts enable toobtain a chiral catalysis which is made obvious by the enantiomericexcesses given in the following table. Chiral Catalyst EnantiomericExcesses LaPTETFSI 69% LaCSTFSI 76% LaMBBMTFSI 72% ScKANTFSI 67%

EXAMPLE 72 Acrylonitrile/4styrenesulfonyl(trifluoromethanesulfonyl)imideCopolymer

A solution of 19.27 g of the lithium salt of4-styrenesulfonyl(trifluoromethanesulfonyl)imide (60 mmoles), 2.12 g (40mmoles) of acrylonitrile and 100 mg of1,1′-azobis)cyclohexanecarbonitrile) (1 mmoles) in 100 ml of anhydroustetrahydrofurane was degassed by flushing with dry argon. Then, underargon, copolymerization of acrylonitrile with the styrene derivative wascarried out by heating the reaction mixture at 60° C. during 48 hours.After cooling, the solution was concentrated, and the polymer wasrecovered by reprecipitation in ether. After filtration and drying,17.54 g of the lithium salt ofpoly(acrylonitrile-co-4-styrenesulfonyl-(trifluoromethanesulfonyl)imide(PANSDTFSI) were recovered with a yield of 82%.

This polymer may be used for preparing gelled polymer electrolytes withfixed anions, the polymer ensuring a double matrix functionalityenabling to obtain the polyelectrolyte gel.

A gel electrolyte consisting of 30 weight percent of polyelectrolyte,35% of ethylene carbonate and 35% of propylene carbonate was prepared.This gel has good mechanical properties and a conductivity of 9.6×10⁴S·cm⁻¹ at 30° C. The number of cationic transport in this electrolyte is0.85. An electrochemical generator was prepared comprising an anodeconsisting of coke carbon (80% in volume) mixed with the copolymer(PANSDTFSI) as binder (20% by volume), the above gelled electrolyte, anda composite cathode consisting of carbon black (6% by volume), LiNiO₂(75% by volume) and the copolymer (PANSDTFSI) (20% by volume). Thisgenerator has good performances in cycling at 25° C. (1,000 cycles ofcharge/discharge between 3 and 4.2 V by maintaining a capacity higherthan 80% of the capacity during the first cycle). Also, it has very goodperformances during calls for power due to the fact of the utilizationof fixed anions. The utilization of fixed anions has also enabled toimprove the evolution of the resistance of the interface.

EXAMPLE 73Acrylonitrile/4-styrenesulfonyl(trifluoromethanesulfonyl)imide Copolymer

According to a process similar to the one used in Example 72, acopolymer of acrylonitrile (3% molar) and of the lithium salt of4-styrenesulfonyl(trifluoromethanesulfonyl)-imide (97% molar) wassynthesized.

This copolymer has antistatic properties, contrary to polyacrylonitrile(PAN) which, in the form of alkaline or ammonium salt, is widely used inthe form of textile fibre. Moreover, spinning of this copolymer iseasier than with non-modified PAN.

The copolymer has very good interaction with cationic coloring matterssuch as methylene blue, which makes it a material of interest forcolored textile fibres, the stability of the color being clearlyimproved with respect to the known copolymer of acrylonitrile andmethallylsulfonate.

EXAMPLE 74 Vinylidenefluoride/2,2-fluorovinylsulfonyl-(trifluoromethanesulfonyl)imideCopolymer

In a chemical reactor, there is introduced a solution of 8.43 g (30mmoles) of 2,2-fluorovinylsulfonyl(trifluoromethanesulfonyl)imideobtained in Example 24 and 100 mg of1,1′-azobis(cyclohexane-carbonitrile) in 100 ml of anhydroustetrahydrofurane. After flushing the reactor under argon, there isintroduced with a sieve, 4.48 g of vinylidene fluoride CF₂CH₂ (70mmoles, commercially available from Air Liquide). Copolymerization wasthen carried out under argon by heating the reaction mixture at 60° C.during 48 hours. After cooling, the solution was concentrated, and thepolymer was recovered by reprecipitation in ether. After filtration anddrying, 10.2 g of the lithium salt ofpoly(vinylidenefluoride-co-2,2-ethanesulfonyl(trifluoromethane-sulfonyl)imide(PFVESTFSI) were recovered with a yield of 79%.

This polymer enables production of gelled polymer electrolytes withfixed anions, the polymer ensuring a double functionality of matrixenabling to obtain the gel of polyelectrolytes.

There is prepared a battery of the same type as the one described inExample 72 and analogous performances were obtained.

EXAMPLE 75 AGE/Epoxy-Half TFSI/OE Copolymer

In a chemical reactor, there is introduced a solution of 15.37 g (50mmoles) of the potassium salt of3,4-epoxybutane-1-sulfonyl(trifluoromethanesulfonyl)imide, prepared asin Example 13, and 685 mg (6 mmoles) of allylglycidylether in 100 ml ofanhydrous tetrahydrofurane. After flushing the reactor with argon, thereare introduced with a sieve 6.34 g (146 mmoles) of 1,2-epoxide in 100 μlof a 10⁻² M solution of potassium t-butoxide in THF. Polymerization wasthen carried out under argon by heating the reaction mixture at 60° C.during 48 hours. After cooling, the solution was concentrated, and thepolymer was recovered by reprecipitation in ether. After filtration anddrying, 15.9 g (71% yield) of the potassium salt ofpoly(oxyethylene-co-3,4-epoxybutanesulfonyl-(trifluoromethanesulfonyl)imide-co-allylglycidyl-ether)were recovered.

This polymer enables to prepare gelled polymer electrolytes with fixedanions, the polymer ensuring a double matrix functionality enabling toobtain the gel of polyelectrolytes. It may be crosslinked during theprocess of preparing an electrochemical system containing same.

With this polyelectrolyte, a battery similar to the one described inExample 22 was prepared, which has given similar performances.

EXAMPLE 76 Polysiloxane with Fixed Anions

In a three-neck flask provided with a cooler, a mechanical stirrer and aneutral gas inlet (Argon), 9.5 g of a copolymer of dimethylsiloxane and(hydrogeno) (methyl)-siloxane (HMS 301 25% SiH, M_(W) 1900 Gelest Inc.,Tullytown, Pa., USA) were placed in solution in tetrahydrofurane; 9.13 gof the lithium salt of vinylsulfonyl(trifluoromethanesulfonyl)imide and70 mg of chloroplatinic acid H₂PtCl₆, were then added. The mixture Washeated to reflux during 4 hours. The polymer was then reprecipitated inethanol.

A copolymer of dimethylsiloxane and of the lithium salt of(N-trifluoromethanesulfonyl-ethylsulfonamide)(methyl)-siloxane was thusobtained.

This polymer is soluble in most of the organic solvents, including inamounts >2% in oils or silicon materials, thus giving them antistaticproperties.

EXAMPLE 77 Li/POENV205 Battery

The lithium salt ofdimethylaminosulfonyl-(trifluoromethanesulfonyl)imide, preparedaccording to Example 25, was tested in an electrochemical generatoraccording to the lithium-polymer technology. The generator was preparedby superposing the following layers:

-   -   a stainless steel current collector having a thickness of 2 mm;    -   a cathode consisting of a button shaped film of composite        material having a thickness of 89 μm and consisting of vanadium        dioxide (45% by volume), Shawinigan black (5% by volume) and a        polyethylene oxide of molecular weight M_(W)=3.105 (50% by        volume);    -   an electrolyte consisting of a button shaped film of        polyethylene oxide of molecular weight Mw=5.10⁶ containing the        lithium salt of        dimethylamino-sulfonyl(trifluoromethanesulfonyl)imide at a        concentration O/Li=15/1;    -   an anode consisting of a sheet of metallic lithium having a        thickness of 50 μm;    -   a current collector similar to the above mentioned collector.

The button shaped members constituting the electrodes and theelectrolyte were cut in a glove box and piled in the order indicatedabove. The collectors were then placed on both sides of the pileobtained.

The assembly was sealed in a button shaped battery casing, whichsimultaneously enables to protect the generator from the atmosphere andto exercise a mechanical stress on the films. The battery was thenplaced in an enclosure under argon mounted in a dryer at a temperatureof 60° C. It was then cycled between 1.8 and 3.3 V at a rate of chargeand discharge of C/10 (charged or discharged nominal capacity in 10hours).

The cycling curve is given in FIG. 1. In this figure, the use, U,expressed in % is given in ordinate, and the number of cycles C is givenin abscissae.

EXAMPLE 78 Extrusion

In a Warner & Pfilder extruder, there is introduced under an argonatmosphere, poly (ethylene oxide) of a molecular weight M_(W)=10⁵ in theform of button shaped members 2 mm in diameter and a mixture of thelithium salt of dodecylsulfonyl(trifluoromethanesulfonyl)imide preparedaccording to a process analogous to the one of Example 39, the potassiumsalt of Igepal® CA-520-propylsulfonyl(trifluoromethanesulfonyl)imideprepared by a process analogous to the one of Example 43, vanadium oxideV₂O₅ crushed to a particle size smaller than 5 μm, and carbon black. Themixture of components was then introduced in such proportions thatvanadium oxide represents 40% of the total volume, Shawinigan black 5%,the potassium salt of Igepal®CA-520-propylsulfonyl(trifluoromethanesulfonyl)imide 2%, and the mixturepoly (ethylene oxide)/lithium salt ofdedecylsulfonyl(trifluoromethanesulfonyl)imide 53%, the lithium saltbeing at a concentration O/Li=15/1. The mixture was then extruded at atemperature of 100° C. in the form of a band 14 cm wide and a thicknessof 63 μM. This film which can be used as cathode, was directly placed ona sheet of stainless steel 8 μm thick.

This film of composite cathode was itself covered with a film ofelectrolyte 30 μm thick obtained by extrusion of a mixture of poly(ethylene oxide) of molecular weight M_(W)=3.10⁵ and a lithium salt ofdodecylsulfonyl(trifluoromethanesulfonyl)imide at a concentrationO/Li=45/1.

The mixture was then laminated with a film of lithium 20 μm thick. Thereis thus obtained an electrochemical generator according to thelithium-polymer technology.

The cycling curve of this generator at a rate of charge and discharge ofC/10 is represented in FIG. 2. In this figure, the use, U, expressed in% is given in ordinate, and the number of cycles C is given isabscissae.

The salts of the present invention contain long alkyl chains such as thepotassium salt of Igepal®CA-520-propylsulfonyl(trifluoromethanesulfonyl)imide or the lithium saltof dedecylsulfonyl(trifluoromethanesulfonyl)imide, enabling toplasticize poly (ethylene oxide). They also facilitate the extrusion offilms of cathodes or electrolytes used during the manufacture ofbatteries according to the technology of lithium-polymer in thin film.Their electrochemical stability also enables to obtain good performancesduring the cycling of these batteries.

1. Ionic compound consisting of an amide or salts thereof, comprising ananionic part associated with at least one cationic part M^(+m) insufficient number to ensure an electronic neutrality thereto,characterized in that M is a hydroxonium, a nitrosonium NO⁺, an ammonium—NH₄ ⁺, a metallic cation having a valency m, an organic cation having avalency m or an organo-metallic cation having a valency m, an organiccation having a valency m or an organo-metallic cation having a valencym and in that the anionic part corresponds to the formulaR_(F)—SO_(x)—N⁻Z in which: the group —S(O)_(x) represents a sulfonicgroup —SO₂— or a sulfinyl group —SO—; R_(F) is a halogen or aperhalogenated alkyl, alkylaryl, oxa-alkyl, aza-alkyl or thia-alkylradical, or a radical corresponding to one of the formulae R_(A)CF₂—,R_(A)CF₂CF₂—, R_(A)CF₂CF(CF₃)— or CF₃C(R_(A))F— in which R_(A)—represents a non-perhalogenated organic radical; Z represents anelectro-attractor radical having a Hammett parameter at least equal tothat of a phenyl radical, selected from: j) —CN, —NO₂, —SCN, —N₃, —CF₃,R′_(F)CH₂— (R′_(F) being a perflourinated radical), flouroalkyloxy,flouroalkylthioxy radical, jj) radicals comprising one or more aromaticnuclei possibly containing at least one hydrogen, oxygen, sulfur orphosphorus atom, said nuclei possibly being condensed nuclei and/or saidnuclei possibly carrying at least one substituent selected fromhalogens, —CN, —NO₂, —SCN, —N₃, —CF₃, CF₃CH₂—, CF₂═CF—O—, CF₂═CF—S—,perflouroalkyl groups, flouroalkyloxy groups, flouroalkylthioxy groups,alkyl, alkenyl, oxa-alkyl, oxa-alkenyl, aza-alkyl, aza-alkenyl,thia-alkyl, thia-alkenyl radicals, polymer radicals, radicals having atleast one cationic ionophoric group and/or at least one anionicionophoric group; with the proviso that a substituent Z may be amonovalent radical, part of a multivalent radical carrying a pluralityof groups R_(F)—S(O), —N—, or a polymer segment; or Z is a radicalR_(D)—Y— in which Y is a sulfonyl, sulfinyl or phosphonyl group andR_(D) is a radical selected from the group consisting of: a) alkyl oralkenyl radicals, aryl, arylalkyl, alkylaryl or alkenylaryl radicals,alicyclic or heterocyclic radicals, including polycyclic radicals; b)alkyl or alkenyl radicals comprising at least one functional ether,thioether, amine, imine, carboxyl, carbonyl, hydroxy, silyl, isocyanateor thioisocyanate group; c) aryl, arylalkyl, arylalkenyl, alkylaryl oralkenylaryl radicals, in which the aromatic nuclei and/or at least onesubstituent of the nucleus comprises heteroatoms such as nitrogen,oxygen, sulfur; d) radicals comprising condensed aromatic cycles whichpossibly comprise at least one heteroatom selected from nitrogen,oxygen, sulfur; e) halogenated alkyl, alkenyl, aryl, arylalkyl,alkylaryl or alkenylaryl radicals in which the number of carbon atomscarrying at least one halogen is at least equal to the number ofnon-halogenated carbon atoms, the carbon in a position of group Y notbeing halogenated when Y is —SO₂—, said radicals possibly comprisingfunctional ether, thioether, amine, imine, carboxyl, carbonyl, hydroxy,silyl, isocyanate or thioisocyanate groups; f) radicalsR_(C)C(R′)(R″)—O— in which R_(C) is an alkyl perfluorinated radical andR′ and R″ are independently from one another, an hydrogen atom or aradical as defined in a), b), c) or d) above; g) radicals (R_(B))₂N—, inwhich the R_(B), identical or different, are such as defined in a), b),c), d) or e) above, one of the R_(B) may be a hydrogen atom, or the tworadicals R_(B) together form a bivalent radical which forms a cycle withN; h) radicals consisting of a polymer chain; i) radicals having one ormore cationic ionophoric groups and/or one or more anionic ionophoricgroups; with the proviso that a substituent R_(D) may be a monovalentradical, part of a multivalent radical carrying a plurality of groupsR_(F)—S(O)_(x)—N—Y—, or a segment of a polymer; with the proviso that,when Y is a sulfonyl or a carbonyl, and R_(D) is a radical such asdefined in a), R_(F) is R_(A)CF₂—, R_(A)CF₂CF₂—, R_(A)CF₂CF(CF₃)—,CF₃C(R_(A))F— or a perhaloalkyl radical having 1 to 2 carbon atoms.2.-78. (canceled)